Effect of whole catchment liming on the episodic acidification of two adirondack streams

During the fall of 1989 7.7Mg/ha of calcium carbonate was applied on two tributary catchments (40 ha and 60 ha) to Woods Lake, a small (25 ha) acidic headwater lake in the western Adirondack region of New York. Stream-water chemistry in both catchment tributaries responded immediately. Acid-neutralizing capacity (ANC) increased by more than 200 eq/L in one of the streams and more than 1000 eq/L in the other, from pre-liming values which ranged from –25 to +40 eq/L. The increase in ANC was primarily due to increases in dissolved Ca²⁺ concentrations. Most of the initial response of the streams was due to the dissolution of calcite that fell directly into the stream channels and adjacent wetlands. A small beaver impoundment and associated wetlands were probably responsible for the greater response observed in one of the streams.After the liming of subcatchmentIV (60 ha), Ca²⁺ concentrations increased with increasing stream discharge in the stream during fall rain events, suggesting a contribution from calcite dissolved within the soil and transported to the stream by surface runoff or shallow interflow. Concentrations of other ions not associated with the calcite (e.g. Na⁺) decreased during fall rain events, presumably due to mixing of solute-rich base flow with more dilute shallow interflow. The strong relation between changes in Ca²⁺ and changes in NO ₃ ^– concentrations during spring snowmelt, (r² = 0.93, slope = 0.96, on an equivalent basis) suggests that both solutes had a common source in the organic horizon of the soil. Increases in NO ₃ ^– concentrations during snowmelt were balanced by increases in Ca²⁺ that was released either directly from the calcite or from exchange sites, mitigating episodic acidification of the stream. However, high ambient NO ₃ ^– concentrations and relatively low ambient Ca²⁺ concentrations in the stream during the spring caused the stream to become acidic despite the CaCO₃ treatment.In stream WO2 (40ha), Ca²⁺ concentrations were much higher than in stream WO4 because of the dissolution of calcite which fell directly into the upstream beaver pond and its associated wetlands. Calcium concentrations decreased as both NO ₃ ^– concentrations and stream discharge increased, due to the dilution of Ca-enriched beaver pond water by shallow interflow. Despite this dilution, Ca²⁺ concentrations were high enough to more than balance strong acid anion (SO ₄ ^– , NO ₃ ^– , Cl^–) concentrations, resulting in a positive ANC in this stream throughout the year. These data indicate that liming of wetlands and beaver ponds is more effective than whole catchment liming in neutralizing acidic surface waters.     

The impacts of a watershed CaCO3 treatment on stream and wetland biogeochemistry in the Adirondack Mountains

Temporal and longitudinal variations in the chemistry of two tributary streams of Woods Lake in the Adirondack Mountains of New York were monitored before and after a watershed CaCO₃ application. One subcatchment of the lake had a large beaver pond and wetland at its headwaters, while the second was free-flowing. Treatment of both subcatchments with CaCO₃ resulted in an immediate increase in acid neutralizing capacity (ANC) associated with Ca²⁺ release. The extent and duration of the response to the treatment were greater in the wetland-impacted stream. Aluminum was retained and complexed with organic solutes generated within the beaver-pond. In the free-flowing stream, NO ₃ ^– concentration increased significantly after the manipulation; this pattern was not evident in the wetland-impacted stream. Net retention of SOkinf4/sup2– was evident in the beaver pond prior to and following treatment, and this response was enhanced after the watershed liming. Comparisons of beaver pond inlet/outlet concentrations, mass balance calculations, and in-pond profiles of chemical parameters revealed patterns of retention of SO ₄ ^2– , NO ₃ ^– and Al, and release of Fe²⁺, dissolved organic carbon (DOC) and NH ₄ ⁺ in the wetland during the summer before CaCO₃ treatment. Post-treatment releases of Ca²⁺ from the near-sediment zone in the beaver pond corresponded to anoxic periods in mid- to late-summer and under ice in winter. These findings demonstrate the importance of increased microbial processing of organic matter, along with high partial pressure Of CO₂ (Pco₂) in facilitating the dissolution of the applied CaCO₃. Dissolved silica (H₄SiO₄) was retained in the wetland during the summer prior to treatment but was released after the manipulation. This phenomenon may reflect the dissolution of diatom frustules or silicate minerals in the wetland at higher pH and DOC concentrations. Within two years of the CaCO₃ treatment 60% of the CaCO₃ applied to the beaver pond and surrounding wetland was dissolved and transported from the pond, in contrast to only 2.2% of the CaCO₃ applied to the upland subcatchment draining into the wetland. These results, coupled with high quantities of exchangeable Ca²⁺ found in sediments and onSphagnums mosses in the pond, demonstrate the importance of hydrologic source areas and wetlands in facilitating the dissolution of added CaCO₃ and in regulating the production of chemical species important in ANC generation.     

Forest soil solutions: Acid/base chemistry and response to calcite treatment

Soil solution chemistry was investigated at a forested watershed draining into Woods Lake. N.Y. as part of the Experimental Watershed Liming Study (EWLS). The objective of this study was to assess the response of soil water to watershed treatment of calcite (CaCO₃). This material was applied in an effort to mitigate the effects of acidic atmospheric deposition. Soil solutions draining Oa and Bs horizons in reference subcatchments were characterized by low pH and acid neutralizing capacity (ANC) due to elevated concentrations of SO ₄ ^2– , NO ₃ ^– and organic anions relative to the sum of base cation (C_B Ca²⁺, Mg²⁺, Na⁺, K⁺) concentrations. Seasonal and spatial variation of pH andANC in soil solutions appeared to belargely controlled by variations in the concentrations of dissolved organic acids which, in turn, were regulated by reactions of Al with soil organic matter. Nitrate was positively correlated and SO²⁺ was negatively correlated with Ca²⁺ and Al concentrations in reference soil solutions, indicating that changes in NO ₃ ^– influences spatial and seasonal variations in Ca²⁺ and Al concentrations. On this basis, NO ₃ ^– appears to be important in soil acidification and the dynamics of drainage water acidity. Comparison of our results with historical data for the site showed declines in concentrations of SO ₄ ^2– , which are consistent with decreases in emissions of SO₄, in the eastern U.S. and atmospheric deposition of SO ₄ ^2– , to the Adirondack region. Mineral soil solutions have shown large increases in concentrations of NO ₃ ^– . Declines in concentrations of C_B and increases in concentrations of Al have occurred over the last ten years, suggesting depletion of soil pools of exchangeable basic cations and increased sensitivity to acidic deposition. Calcite (CaCO₃) treatment of 6.89 Mg/ha resulted in a significant increase of Ca²⁺, ANC and pH in both Oa and Bs horizon soil solutions. Soil water response to CaCO₃ addition was most evident during the first year after treatment, apparently due to macropore transport of particulate and dissolved CaCO₃ However, increases in ANC and pH in the mineral soil waters were not sustained and appeared insufficient to result in substantial improvement in surface water quality over the 43 month study period.     

Processes regulating temporal and longitudinal variations in the chemistry of a low-order woodland stream in the Adirondack region of New York

Watershed processes influence the acid neutralizing capacity of surface waters by mediating changes in concentration of ionic solutes. Acidification of surface waters by atmospheric deposition of mineral acids and the extent to which ecosystem transformations neutralize this acidity are of particular concern. Seasonal variations in flow paths of water through soil and biological processes result in short-term changes in chemistry that may be critical to surface water ecology. In this study, we assessed longitudinal and temporal variations in the chemistry of a low-order stream, Pancake-Hall Creek, located in the west-central Adirondack region of New York. By quantifying changes in ionic solute concentration (e.g. Ca²⁺, Al^a+, SO ₄ ^2– , NO ₃ ^– ) we were able to evaluate processes responsible for short-term fluctuations in acid/base chemistry.In the headwater sites, stream water was acidic; changes in pH, acid neutralizing capacity (ANC) and Al were primarily due to seasonal variations in basic cation and NO ₃ ^– concentrations. At the downstream sites, water migrated through a large beaver impoundment and thick till resulting in higher pH, acid neutralizing capacity and basic cation concentrations, and lower concentrations of Al. Neutralization of acidity was particularly evident during the low flow summer period and coincided with retention of SO ₄ ^2– in the beaver impoundment. During the high flow non-summer (October to June) period, depressed pH and ANC, and elevated Al concentrations were observed in the downstream sites. Acidic conditions during the non-summer period were not due to the oxidation of reduced sulfur deposits (e.g. SO ₄ ^2– events) but rather the resumption of conservative SO ₄ ^2– transport through the beaver impoundment (e.g. minimal SO ₄ ^2– retention) coupled with increases in NO ₃ ^– .     

The experimental watershed liming study: Comparison of lake and watershed neutralization strategies

The Experimental Watershed Liming Study (EWLS) was initiated to evaluate the application of CaCO₃ to a forested watershed in an effort to mitigate the acidification of surface water. The objective of the EWLS was to assess the response of the Woods Lake watershed to an experimental addition of CaCO₃. During October 1989, 6.89 Mg CaCO₃/ha was applied by helicopter to two subcatchments comprising about 50% (102.5 ha) of the watershed area. The EWLS involved individual investigations of the response of soil and soil water chemistry, forest and wetland vegetation, soil microbial processes, wetland, stream and lake chemistry, and phytoplankton and fish to the CaCO₃ treatment. In addition, the Integrated Lake/Watershed Acidification (ILWAS) model was applied to the site to evaluate model performance and duration of the treatment. The results of these studies are detailed in this volume. The purposes of this introduction and synthesis paper are to: 1) present the overall design of the EWLS, 2) discuss the linkages between the individual studies that comprise the EWLS, and 3) summarize the response of the lakewater chemistry to watershed addition of CaCO₃ and compare these results to previous studies of direct lake addition. An analysis of lake chemistry revealed the watershed treatment resulted in a gradual change in pH, acid neutralizing capacity (ANC) and Ca²⁺ in the water column. This pattern was in contrast to direct lake additions of CaCO₃ which were characterized by abrupt changes following base addition and subsequent rapid reacidification. Over the three-year study period, the supply of ANC to drainage waters was largely derived from dissolution of CaCO₃ in wetlands. Relatively little dissolution of CaCO₃ occurred in freely draining upland soils. The watershed treatment had only minor effects on forest vegetation. The watershed treatment eliminated the episodic acidification of streamwater and the near-shore region of the lake during snowmelt, a phenomenon that occurred during direct lake treatments. Positive ANC water in the near-shore area may improve chemical conditions for fish reproduction, and allow for the development of a viable fish population. The watershed CaCO₃ treatment also decreased the transport of Al from the watershed to the lake, and increased the concentrations of dissolved organic carbon (DOC) and dissolved silica (H₄SiO₄) in stream and lakewater. The watershed treatment appeared to enhance soil nitrification, increasing concentrations of NO₃ ^– in soilwater and surface waters. However, the acidity associated with this NO₃ ^– release was small compared to the increase in ANC due to CaCO₃ addition and did not alter the acid-base status of Woods Lake. Acid neutralizing capacity (ANC) budgets for 12-month periods before and after the watershed treatment showed that the lake shifted from a large source of ANC to a minor source due to retention of SO₄ ^2–, NO₃ ^–, Al and the elevated inputs of Ca²⁺ associated with the watershed CaCO₃ application. In contrast to the direct lake treatments, Ca²⁺ inputs from the watershed application were largely transported from the lake.     

Peat and solution chemistry responses to CaCO3 application in wetlands next to Woods Lake,New York

We studied the effect of a calcite (CaCO₃) treatment on peat and pore water chemistry in poor fen and conifer swamp wetlands next to Woods Lake and its tributaries to evaluate the role of wetlands in an Experimental Watershed Liming Study (EWLS). Peat was characteristically organic rich and nutrient poor, with exchangeable Ca concentrations of < 13 cmol_ckg^–1. We estimated that between 0.4 to 4 Mg (CaCO₃) ha^–1 fell directly on three study sites; however, one year after the treatment the increase in Ca concentration (0–8 cm depth) was equivalent to a (CaCO₃) dosage of 3 Mg ha^–1 with an additional 2–4 Mg ha^–1 of undissolved (CaCO₃) still present, suggesting the peat retained Ca supplied from uplands. Most aspects of peat chemistry including microbial respiration and SO₄ reduction did not respond to the treatment.Peat pore water (5 and 20 cm depths) had a mean pH of 4.82 before treatment with high concentrations of dissolved organic carbon (DOC mean of 790 mol C/l) and low Ca²⁺ concentration (mean of 32 mol/l). The (CaCO₃) treatment increased concentrations of Ca²⁺ to a mean of 87 mol/l and dissolved inorganic carbon (DIC) from 205 to a mean of 411 mol/l, whereas it decreased monomeric Al concentration from 19 to 10 mol/l. Otherwise, pore water chemistry showed little response to the treatment, at least within natural spatial and temporal variation of solute concentrations. The results suggest that liming watersheds with the relatively low (CaCO₃) dosage applied in this study can benefit acidic waters downstream by exporting more Ca and DIC and less monomeric Al, with otherwise little effect on the peat itself.     

Calcium content of liming material and its effect on sulphur release in a coniferous forest soil

Soil columns with O + A (Experiment I) or Ohorizons (Experiment II) from a Haplic Podsol wereincubated at 15 °C for 368 and 29 + 106 days,respectively. Three types of liming material differingin Ca²⁺ content, i.e. calcium carbonate(CaCO₃), dolomite (CaMg(CO₃)₂) andmagnesium carbonate (MgCO₃), were mixed into theO horizons in equimolar amounts corresponding to 6000kg of CaCO₃ per ha. In the limed treatments ofExperiment I, the leaching of dissolved organic carbon(DOC) and the net sulphur mineralization (estimated asaccumulated SO ₄ ^2– leaching corrected forchanges in the soil pools of adsorbed and waterextractable SO ₄ ^2– ) increased with decreasingCa²⁺ content of the lime and increasing degree oflime dissolution. In relation to the controltreatment, only the MgCO₃ treatment resulted ina significantly higher net sulphur mineralization. InExperiment I the net sulphur mineralization was 4.06,1.68, 0.57, and 2.14 mg S in the MgCO₃,CaMg(CO₃)₂, CaCO₃ and control treatment,respectively. The accumulated SO ₄ ^2– leachingin Experiment II during the first 29 days was 1.70,0.74 and 0.48 mg S in the MgCO₃,CaMg(CO₃)₂ and control treatment,respectively. In the two experiments there wereconsistently significant positive correlations betweenleached amounts of SO ₄ ^2– and DOC. It wasconcluded that net sulphur mineralization was stronglyconnected to the solubilization of the organic matter(DOC formation) and that pH and/or Ca²⁺ ionsaffected the net sulphur mineralization through theireffects on organic matter solubility.     

Chloride-dependent sodium and water transport in the seawater eel intestine

Summary Simultaneous measurements of transepithelial potential difference (PD) and net water flux were made in the stripped seawater eel intestine, and the effects of removal of Ca²⁺ and replacement of Cl^– with other anions on these two parameters were examined. Removal of Ca²⁺ from normal (NaCl) Ringer solution on both mucosal and serosal sides reduced the serosa-negative PD and the net water flux. Since SO ₄ ^2– binds Ca²⁺ strongly, the effects of substitution of SO ₄ ^2– for Cl^– could be due to deficiency in both Cl^– and Ca²⁺. Among five anions used in this study, CH₃SO ₄ ^– (with low affinity to Ca²⁺) seems to be the most suitable substitute for Cl^–. When both mucosal and serosal Cl^– were replaced with CH₃SO ₄ ^– , both the PD and the net water flux decreased to approximately zero. When mucosal Cl^– was replaced progressively with other anions, the serosa-negative PD and the net water flux decreased in association with the decrease in Cl^– concentration, and a linear regression was observed between the decrease in the net water flux and that in the PD. These results indicate that Na⁺ and water transport depend closely on Cl^– transport.     

Solution chemistry profiles of mixed-conifer forests before and after fire

Solution chemistry profiles of mixed-conifer forests in granitic catchments of the Sierra Nevada were measured for three years before (1987–1990) and three years after (1990–1993) prescribed fire. Wet deposition, throughfall and soil solution samplers were installed in both white-fir and giant-sequoia dominated forest stands underlain by poorly developed inceptisols. Stream water chemistry was monitored as part of an ongoing study of catchment outputs. Calcium, NO ₃ ^– and Cl^– were the major ions in precipitation. Canopy leaching increased mean concentrations of all major ions, especially K⁺ and Ca²⁺. Water flux through the soil occurred largely during spring snowmelt. Forest floor leachate represented the most concentrated solutions of major ions. Interaction with the mineral soil decreased mean concentrations of most species and the average composition of soil solutions closely resembled stream water at baseflow. Bicarbonate alkalinity, Ca²⁺, Mg²⁺, and Na⁺ were enriched in stream water relative to precipitation whereas inputs of H⁺, NH ₄ ⁺ , NO ₃ ^– and SO ₄ ^2– were retained within the catchments.Burning of the forest understory and litter layer increased solute concentrations in soil solution and stream water. Mean soil solution Ca²⁺, Mg²⁺ and K⁺ concentrations increased more than 10 fold, but the relative predominance of these cations was not affected by burning. Sulfate concentration, which was very low in soil solutions of undisturbed stands (<25 mmol_c m^–3), increased more than 100 times following fire. Ammonium concentration exhibited a rapid, short-term increase and then a decrease below pre-burn levels. Changes in soil solution chemistry were reflected in catchment outputs.Corresponding author.     

Longitudinal and seasonal patterns of stream acidity in a headwater catchment on the Appalachian Plateau, West Virginia, U.S.A.

The chemical composition during baseflow was used to elucidate the fundamental processes controlling longitudinal and seasonal patterns of stream acidity in Yellow Creek, a chronically acidic headwater (pH range 3.7--4.2) on the Appalachian Plateau in northeastern West Virginia. Sulfate concentrations controlled the variability of stream acidity within the Yellow Creek catchment. Decreases in stream free H⁺ acidity with decreasing elevation likely resulted from SO ₄ ^2– retention in riparian wetland areas as well as spatial variation in dominant tree species. Seasonal variations in free H⁺ and inorganic monomeric aluminum (Alⁿ⁺) concentrations appeared related to seasonal fluctuations in baseflow discharge which was controlled by vegetative activity. Baseflow stream discharge, as well as H⁺ and Alⁿ⁺ acidity, gradually declined during the growing season (June through October), likely reflecting microbial SO ₄ ^2– > reduction in saturated anaerobic environments within riparian wetlands. A marked pulse of stream H⁺, Alⁿ⁺, and SO ₄ ^2– coincided with an abrupt increase in baseflow discharge resulting from the cessation of transpiration after leaf-fall in November. This seasonal pattern suggests that autumn may be a critical period for eastern brook trout in streams draining wetlands on the Appalachian Plateau.     

Processes affecting the response of sulfate concentrations to clearcutting in a northern hardwood forest, Catskill Mountains, New York, U.S.A.

The effects of disturbance on the biogeochemical processes that affect the sulfur (S) cycle in forested ecosystems are important, but have been studied in only a few locations. In this investigation, the mechanisms that caused large decreases in stream SO ₄ ^2– concentrations after clearcutting a small forested catchment in the Catskill Mountains of southeastern New York in 1997 were identified through an examination of pH and SO ₄ ^2– concentrations in soil solutions, bulk deposition of SO ₄ ^2– in throughfall collectors, adsorbed SO ₄ ^2– concentrations in buried soil bags, and spatial variations in SO ₄ ^2– concentrations in shallow groundwater. The load of SO ₄ ^2– –S in stream water during the first 2 years after clearcutting was about 2 kg ha^–1 year^–1 less than the background value of 8–10 kg ha^–1 year^–1. The 10 and 19% decrease in net throughfall flux of SO ₄ ^2– –S during the 2nd and 3rd year after the clearcut, respectively, reflects reduced dry deposition of S after removal of the canopy, but this decrease accounts for 0 and 43%, respectively, of the decrease in SO ₄ ^2– load in streamflow for these 2 years. The pH of B-horizon soil water decreased from 4.5 to 4.0 within 8 months after the clearcut, and SO ₄ ^2– concentrations decreased from 45 µmol L^–1 to less than 20 µmol L^–1 during this time. A strong correlation between SO ₄ ^2– concentrations and pH values (r ² = 0.71, p < 0.01) in B-horizon soil water during the post-harvest period (1997–1999) reflects increased SO ₄ ^2– adsorption in response to soil acidification. Sulfate concentrations in groundwater from 21 spatially distributed wells were inversely related to a topographic index that served as a surrogate for soil wetness; thus, providing additional evidence that SO ₄ ^2– adsorption was the dominant cause of the decreased SO ₄ ^2– concentrations in the stream after clearcutting. These results are consistent with those from a 1985 whole-tree harvest at the Hubbard Brook Experimental Forest in New Hampshire in which increased SO ₄ ^2– adsorption resulting from decreased soil pH was the primary cause of decreased SO ₄ ^2– concentrations in stream water.     

Metal requirement of the isolated red cell Ca-pump ATPase after elimination of calmodulin dependence by trypsin attack

Mild proteolysis by trypsin activates the purified (Ca²⁺ + Mg²⁺) - ATPase protein from human red cells in a way which is similar to the effect obtained by addition of calmodulin. The trypsin concentration required to reach half maximal effect in 3 minutes at 37°C is 2.5 – 3.5 μg/ml. SDS-poly-acrylamide gel electrophoresis reveals a degradation of the main protein (150'000 Dalton) into a large fragment (95'000 – 100'000 Dalton) and a small fragment (35'000 – 40'000 Dalton). Increasing ATPase activity correlates with the degree of proteolysis.The _Ca of the digested (Ca²⁺ + Mg²⁺)-ATPase is 0.85 ± 0.1 μM Ca²⁺ as compared to 8.0 ± 0.75 μM Ca²⁺ before digestion and is statistically significantly different from _Ca = 1.66 ± 0.22 μM Ca²⁺ observed in activation by a saturating calmodulin concentration. Addition of calmodulin to the trypsinized enzyme has neither an effect on the Ca²⁺-affinity nor achieves any large increase of the maximal rate.High Ca²⁺ concentrations (above 0.05 – 0.1 mM) after trypsin treatment still inhibit the (Ca²⁺ + Mg²⁺)-ATPase activity. Mg²⁺ activates in the same concentration range ( _Mg = 25 μM) as in the undigested preparation ( _Mg = 27 μM) and retains its competitive behaviour towards Ca²⁺ after trypsin treatment.It is concluded that (1) trypsin treatment unmasks high affinity sites for Ca²⁺ ( _Ca 1 μM) and that, therefore, such sites are not added to the system by calmodulin, and (2) that inhibition by high Ca²⁺-concentrations is not due to Ca - Mg competition at sites located on the calmodulin molecule.     

Buffering an Acidic Stream in New Hampshire with a Silicate Mineral

Ground and pelletized Wollastonite (Wo; CaSiO₃) was added to a 50‐m reach of an anthropogenically acidified stream within the Hubbard Brook Experimental Forest, New Hampshire, to evaluate its buffering and restoration potential. The Wo was highly effective in raising the pH, acid‐neutralizing capacity (ANC), dissolved inorganic carbon (DIC), and Ca²⁺ concentrations of the stream water, but during the short duration of the experiment had no discernable effect on the stream biota. After initial, spike‐like fluctuations in pH and concentrations of ANC, DIC, and Ca²⁺, the relatively slow dissolution rates of the Wo dampened extreme concentrations and contributed to relatively long‐lasting (4 months) amelioration of streamwater acidity. Changes in concentrations of Ca²⁺, dissolved Si, ANC, and DIC were inversely related to streamflow. After several high, stream‐discharge events, concentrations quickly and consistently returned to pre‐event conditions.     

The major ion chemistry of some southern African saline systems

Africa south of about 23° S has few natural athalassic lakes, saline or freshwater. South Africa, however, is rich in temporary pans, many of which are saline, while permanent saline springs occur along the coastal strip of the Namib Desert in Namibia. This paper examines the chemistry of the major ions in 67 Namibian waters, 47 of which have not previously been reported in the literature, and compares them with 66 South African waters, five of which have not previously been reported, and with saline lakes in East Africa.The highest value for total dissolved solids in South African waters was 276 g l^–1 (Koekiespan, south-western Cape) and the highest for Namibian waters were 160 g l^–1 (Hosabes, a small spring on a gypsous crust) and 302 g l^–1 (a salt pan at Oranjemund at the mouth of the Orange River). The dominant ions in fresh waters in the region are Ca²⁺ and HCO _inf3 ^– /CO _inf3 ^2– in the interior and in Namibia, and Na²⁺ and Cl⁺ on the south and east coasts. Regardless of the geochemistry of their substrata, the dominant ions in the saline waters throughout the region are Na⁺ and Cl^–. Thus differential precipitation of CaCO₃ and CaSO₄, as a result of evaporative concentration at high salinities, appears to be the determinant of the proportions of the major ions in these systems.The permanent springs on gypsous crusts along the coast of Namibia, although dominated by Na⁺ and Cl^– ions, contain considerable quantities of both Ca²⁺ and SO ₄ ^2– ions.     

Different secretory actions of pancreastatin in bovine and human parathyroid cells

Chromogranin A is an acidic protein that is costored and cosecreted with parathyroid hormone (PTH) from parathyroid cells. Pancreastatin (PST), is derived from chromogranin A, and inhibits secretion from several endocrine/neuroendocrine tissues. Effects of different pancreastatin peptides were investigated on dispersed cells from bovine and human parathyroid glands. Bovine PST(1–47) and bovine PST(32–47) inhibited PTH release from bovine cells in a dose-dependent manner. The former peptide was more potent and suppressed the secretion at 1–100 nM. This inhibition was evident in 0.5 and 1.25 mM, but not in 3.0 mM external Ca²⁺. Both peptides failed to alter the concentration of cytoplasmic Ca²⁺([Ca²⁺]_i) of bovine cells. Human PST(1–52) and PST(34–52) did not affect PTH release or [Ca²⁺]_i of parathyroid cells from patients with hyperparathyroidism, nor [Ca²⁺]_i of normal human parathyroid cells. Furthermore, bovine PST(1–47) and bovine PST(32–47) failed to alter the secretion of abnormal human parathyroid cells. The study indicates that PST exerts secretory inhibition on bovine but not human parathyroid cells, and that this action does not involve alterations of [Ca²⁺]_i.     

Small scale pH buffering in organic horizons of two boreal coniferous forest stands

Factors behind the small-scale variaton of pH were examined in O horizons (humus layers) developed under two stands of Picea abies (L.) Karst. (Site F and K) by combining data on the composition of the cation exchange complex with data from titrations of corresponding H⁺-saturated samples. Cations extractable in 0.5 M CuCl₂ (S=cmol_c kg^–1 [2Ca+2Mg+2Mn+K+Na]), aluminium extractable in 1.0 M KCl (Al_e=cmol_c kg^–1 [3Al]) and in 0.5 M CuCl₂ (Al_org=cmol_c kg^–1 [3Al]), as well as pH measured in 0.01 M CaCl₂ (pH_Ca) were analysed in one-cm-layers of 13 O horizon cores at each site. Composite samples representing each of the one-cm-layers at each site, as well as samples with two different levels of Al saturation at Site K, were H⁺ saturated and titrated with NaOH to chosen end points of pH_Ca=4.0 and 5.5 in a 0.01 M CaCl₂ ionic medium. The Acid Neutralisation Capacity (ANC) was estimated as the amount of base needed to increase pH_Ca of the composite H⁺-saturated samples to the mean pH_Ca of the corresponding natural samples. The ANC was found to be similar in magnitude or higher than the amount of sites binding S+Al_e, which suggests that 1.0 M KCl exchangeable Al ions are nonacidic in acid O horizons. The relative contribution from i) the capacity of acidic functional groups, ii) their acid strength and iii) their degree of neutralisation to differences in pH_Ca between sites, among cm-layers and between samples with different levels of Al saturation were estimated from titration curves adjusted to hold two out of three factors (i, ii and iii) to be constant. The degree of neutralisation explained most of the differences in pH_Ca between the two sites, as well as between samples with different levels of Al saturation at Site K. The pH_Ca decrease by depth at site F was, however, partly explained by an increasing acid strength. The study emphasizes the importance of examining not only changes in the degree of neutralisation, but also changes in the acid strength and the capacity of buffering functional groups before conclusions about causes behind acidification processes can be made. Difficulties of accurately estimating the degree of neutralisation (base saturation) of acidic functional groups from the composition of adsorbed cations, owing to the unknown acidity of adsorbed Al, was also demonstrated.     

Electrogenic calcium transport in plasma membrane of rat pancreatic acinar cells

Summary ATP-dependent⁴⁵Ca²⁺ uptake was investigated in purified plasma membranes from rat pancreatic acinar cells. Plasma membranes were purified by four subsequent precipitations with MgCl₂ and characterized by marker enzyme distribution. When compared to the total homogenate, typical marker enzymes for the plasma membrane, (Na⁺,K⁺)-ATPase, basal adenylate cyclase and CCK-OP-stimulated adenylate cyclase were enriched by 43-fold, 44-fold, and 45-fold, respectively. The marker for the rough endoplasmic reticulum was decreased by fourfold compared to the total homogenate. Comparing plasma membranes with rough endoplasmic reticulum, Ca²⁺ uptake was maximal with 10 and 2 mol/liter free Ca²⁺, and half-maximal with 0.9 and 0.5 mol/liter free Ca²⁺. It was maximal at 3 and 0.2 mmol/liter free Mg²⁺ concentration, at an ATP concentration of 5 and 1 mmol/liter, respectively, and at pH 7 for both preparations. When Mg²⁺ was replaced by Mn²⁺ or Zn²⁺ ATP-dependent Ca²⁺ uptake was 63 and 11%, respectively, in plasma membranes; in rough endoplasmic reticulum only Mn²⁺ could replace Mg²⁺ for Ca²⁺ uptake by 20%. Other divalent cations such as Ba²⁺ and Sr²⁺ could not replace Mg²⁺ in Ca²⁺ uptake. Ca²⁺ uptake into plasma membranes was not enhanced by oxalate in contrast to Ca²⁺ uptake in rough endoplasmic reticulum which was stimulated by 7.3-fold. Both plasma membranes and rough endoplasmic reticulum showed cation and anion dependencies of Ca²⁺ uptake. The sequence was K⁺>Rb⁺>Na⁺>Li⁺>choline⁺ in plasma membranes and Rb⁺K⁺Na⁺>Li⁺>choline⁺ for rough endoplasmic reticulum. The anion sequence was Cl^–Br^–I^–>SCN^–>NO ₃ ^– >isethionate^– >cyclamate^–>gluconate^–>SO ₄ ^2– glutarate^– and Cl^–>Br>gluconate>SO ₄ ^2– >NO ₃ ^– >I^–>cyclamate^–SCN^–, respectively. Ca²⁺ uptake into plasma membranes appeared to be electrogenic since it was stimulated by an inside-negative K⁺ and SCN diffusion potential and inhibited by an inside-positive diffusion potential. Ca²⁺ uptake into rough endoplasmic reticulum was not affected by diffusion potentials. We assume that the Ca²⁺ transport mechanism in plasma membranes as characterized in this study represents the extrusion system for Ca²⁺ from the cell that might be involved in the regulation of the cytosolic Ca²⁺ level.     

Composition and dynamics of epilithic algae in a forest stream at Shillong (India)

The seasonal dynamics of epilithic algae in a third order pristine forest stream were analyzed over a period of 2 years. Stream water was slightly acidic and nutrient poor. Encrusting, filamentous flocs, and filaments were found. Algal standing crop was high (mean concentration of Chl a 16–43 mg m^–2) in spring. Filamentous algae contributed most to standing crop. Diatoms made up over 85% by number of the epilithon. Blue-greens were abundant upstream, and chlorophytes downstream. This shift was ascribed to greater light availability downstream. The community was more diverse during spring. Water current was the most important variable regulating epilithon structure. Total phosphorus (TP), orthophosphate (O-PO _inf4 ^su3– ), silica (Si⁴⁺), nitrate (NO _inf3 ^su– ) and conductance correlated negatively with flow rate. Green algae showed a positive correlation to phosphorus during low and stable flow. During rapid runoff, diatoms were the most resistant forms. Seasonal change in the epilithic community was mainly regulated by fluctuations in flow rate.     

Biogeochemical evolution of a sulfur-iron rich aquatic system in a reflooded wetland environment (Lake Agmon,northern Israel)

Major biogeochemical processes in the newly created, shallow Lake Agmon (Hula Valley, northern Israel) were investigated from 1994 to 1996. Sediment cores, lake water and porewater were analyzed for chemical composition and spatial distribution. Sediment analyses revealed that Lake Agmon has two different sediment types: peat sediments in the northern and central parts, and marls in the southern part. The basic composition of the lake's water was controlled mainly by the mixing of two distinct water types (Jordan River and water drainage), and by evaporation. About 3/4 of the lake water originated from the Jordan Inlet, a quarter through the Z Canal Inlet (peat drainage) and a minor amount from groundwater seepage. Lake Agmon is unique among freshwater wetlands owing to its high SO ₄ ^2– content, which is ca. 1/3 that of sea water. This characteristic is ascribed to the dissolution of secondary gypsum, formed in the peat soils since the drainage of the historic Hula Marsh. Leaching gypsum from the shallow sediments during the first few months after flooding was followed by a later stage of constant diffusion and advection of SO ₄ ^2– from gypsum dissolution in deeper sediments. Gypsum dissolution in lake sediments contributed ca. half of the SO₄ ^2– and Ca²⁺ inputs to the lake. The concomitant increase of Ca²⁺ combined with alkalinity release due to organic matter decomposition in the sediments led to the precipitation of CaCO₃. This precipitation was enhanced by photosynthesis, particularly during summers, and consumed about a tenth of the Ca²⁺ and third of the alkalinity outputs from the lake. Iron-hydroxide was the main agent for microbial oxidation of organic matter, surpassing by far the role of sulfate, nitrate and manganese as electron acceptors. The produced Fe²⁺ was transported upward by diffusion and advection and oxidized to ferric iron at the sediment-water interface. There is evidence, however, that some sulfate was reduced, but most of the produced sulfide reacted with ferrous iron and accumulated in the sediments as FeS minerals. Therefore, despite high sulfate concentrations, the high iron availability restricted release of toxic sulfides into the water and thereby served to maintain reasonable water quality.     

Photosynthesis,Respiration and Exopolymer Calcium-Binding in Biofilm Calcification (Westerhöfer and Deinschwanger Creek,Germany)

The impact of microbial activity on biofilm calcification in aquatic environments is still a matter of debate, especially in settings where ambient water has high CaCO₃ mineral supersaturation. In this study, biofilms of two CO₂-degassing karst-water creeks in Germany, which attain high calcite supersaturation during their course downstream, were investigated with regard to water chemistry of the biofilm microenvironment. The biofilms mainly consisted of filamentous cyanobacteria (Phormidium morphotype) and heterotrophic bacteria (including sulfate-reducing bacteria), which affect the microenvironment and produce acidic exopolymers. In situ and ex situ microelectrode measurements showed that a strong pH increase, coupled with Ca^{2 +} consumption, occurred in light conditions at the biofilm surface, while the opposite occurred in the dark. Calcite supersaturation at the biofilm surface, calculated from ex situ Ca^{2 +} and CO₃ ^2? microelectrode measurements, showed that photosynthesis resulted in high omega values during illumination, while respiration slightly lowered supersaturation values in the dark, compared to values in the water column. Dissociation calculation demonstrated that the potential amount of Ca^{2 +} binding by exopolymers would be insufficient to explain the Ca^{2 +} loss observed, although Ca^{2 +} complexation to exopolymers might be crucial for calcite nucleation. No spontaneous precipitation occurred on biofilm-free limestone substrates under the same condition, regardless of high supersaturation. These facts indicate that photosynthesis is a crucial mechanism to overcome the kinetic barrier for CaCO₃ precipitation, even in highly supersaturated settings.