The seasonal cycle of inorganic carbon species in Cazenovia Lake,New York, 1977 *

SUMMARY. Spatial and temporal distributions of inorganic carbon and related ionic species (Ca²⁺, H⁺) were monitored weekly for 1 year in Cazenovia Lake, a small mesotrophic marl lake. Attendant [H₂CO*₃]([H₂CO₃] + [CO₂(aq)]) and CaCO₃ equilibrium conditions were determined through application of equilibrium equations adjusted for appropriate temperatures and ionic strength. A seasonal cycle was demonstrated for the inorganic carbon species which was temporally correlated to the lake's thermal and productivity cycles. Vertical homogeneity in carbonate chemistry was evident during turnover periods while dramatic differences developed between the epilimnion and hypolimnion during winter and summer stratification. The lake was supersaturated throughout the year with H₂CO*₃, though saturation was approached during the productive summer months in the epilimnion. The epilimnion was supersaturated with respect to CaCO₃, from the start of spring turnover to the end of autumn turnover. Calcium (Ca²⁺) levels within the epilimnion decreased through much of the same period. Dissolution of CaCO₃ in the hypolimnion is indicated by increases in Ca²⁺ and alkalinity as stratification periods progress. Analysis of potentially influencing factors indicates that the seasonal trends were mostly a result of CO₂ metabolism. This was further supported by concurrent algal biomass and ¹⁴C uptake.     

Induction of Calcium Carbonate by Bacillus cereus

The purpose of this research was to study how the bacteria Bacillus cereus (DCB1) utilizes calcium ions in a culture medium with carbon dioxide (CO₂) to yield calcium carbonate (CaCO₃). The bacteria strain DCB1 was a dominant strain isolated from dolomitic surfaces in areas of Karst topographies. The experimental method was as follows: a modified beef extract-peptone medium (beef extract 3.0 g, peptone 10 g, NaCl 5.0 g, CaCl₂ 2.0 g, glass powder 2.0 g, distilled water 1 L, and a pH between 6.5 and 7.5) was inoculated with B. cereus to attempt to induce the synthesis of CaCO₃. The sample was then processed by centrifugation every 24 h during the 7-day cultivation period. The pH, carbonic anhydrase (CA) activity, and the concentrations of both HCO^- ₃ and Ca²⁺ in the supernatant fluid were measured. Subsequently, precipitation in the culture medium was analyzed to confirm, or otherwise, the presence and if present, the formation, of CaCO₃. Methods used included X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), and Energy Dispersive Spectroscopy (EDS). Meanwhile, the carbon source in the carbonate was classified by its isotope composition. Results showed that B. cereus can improve its pH value in this culture medium; concentrations of HCO^- ₃ and Ca²⁺ showed a significant decline over the duration of the cultivation period. CA activity reached its maximum during the second day; XRD, SEM, TEM, and isotope analysis all revealed the presence of CaCO₃ as a precipitate. Additionally, these results did not occur in an aseptic control group: no detectable level of CaCO₃ was produced therein. In conclusion: B. cereus can metabolize active materials, such as secretase, by its own growth and metabolism, and can either utilize atmospheric CO₂, or respire, to induce CaCO₃ production. Experimental evidence is offered for a concomitant CO₂ reduction and CaCO₃ induction by microorganisms.     

Hydrobiology and organic production in a marl lake of Kashmir Himalayan Valley

L. Naranbagh (alt. 1587 m) is a polymictic, shallow marl lake in the flood-plain valley of Kashmir, India. Macrofloral affinities resemble Potamogeton Type of Forsberg (1965) with alkaline waters, not rich in phosphorus. CaCO₃ precipitation coupled with decline in Ca²⁺ and alkalinity values are characteristic of the lake. Fluctuations in Mg²⁺, Na⁺, K⁺, and Cl^– were relatively conservative. The levels of PO _inf4 ^sup3– -P and NO _inf3 ^sup– -N indicate moderate fertility of the lake water.Persistence of a summer-autumn planktonic algal pulse is related to favourable irradiance, high water temperatures, and increased photosynthetic efficiency values. The most striking seasonality in photosynthetic rates (m^–2 h^–1) between winter minimum (3 mg C_assim) and summer maximum (75.4 mg C_assim) is determined by mainly climatic changes. Energy flow gave annual phytoplankton production of 51.95 × 10² KJ m^–2 for the ecosystem.The nutrient levels and productivity rates suggest mesotrophic status of L. Naranbagh in classic oligoeutrophic classification of lake types.     

Predicting Biogeochemical Calcium Precipitation in Landfill Leachate Collection Systems

Clogging of leachate collection systems within municipal solid waste landfills can result in greater potential for contaminants to breach the landfill barrier system. The primary cause of clogging is calcium carbonate (CaCO_3(s)) precipitation from leachate and its accumulation within the pore space of the drainage medium. CaCO_3(s) precipitation is caused by the anaerobic fermentation of volatile fatty acids (VFAs), which adds carbonate to and raises the pH of the leachate. An important relationship in modeling clogging in leachate collections systems is a yield coefficient that relates microbial fermentation of VFAs to precipitation of calcium carbonate. This paper develops a new, mechanistically based yield coefficient, called the carbonic acid yield coefficient (Y_H), which relates the carbonic acid (H₂CO₃) produced from microbial fermentation of acetate, propionate, and butyrate to calcium precipitation. The empirical values of Y_H were computed from the changes in acetate, propionate, butyrate, and calcium concentrations in leachate as it permeated through gravel-size material. The theoretical and empirical results show that the primary driver of CaCO_3(s) precipitation is acetate fermentation. Additionally, other non-calcium cations (e.g., iron and magnesium) precipitated with carbonate (CO_2-) when present in the leachate. A common yield between total cations bound to CO₃ ^2- and H₂CO₃ produced, called the calcium carbonate yield coefficient (Y_c), can reconcile the empirical yield coefficient for synthetic and actual leachates.     

Seasonal dynamics of phytoplankton and phytobenthos,and associated chemical interactions,in a shallow upland lake (Malham Tarn,northern England)

Seasonal changes of phytoplankton were followed over 3 years (1985–87) in a shallow, unstratified and calcareous upland lake.The phytoplankton was of low to moderate abundance and generally dominated by phytoflagellates. Seasonality involved a winter minimum of abundance, a spring maximum of diatoms, and often brief increases in summer that included blue-greens, especially the colonial Gloeotrichia echinulata. Some components were of benthic origin. Seasonal growth of the main component of the phytobenthos, Chara globularisvar. virgata, caused a regular summer depletion in lake water of Ca²⁺ and HCO₃ ^- (alkalinity) by associated CaCO₃ deposition, and a more extreme (and unusual) depletion of K⁺. Chemical analysis of Chara biomass and of underlying sediments indicated a large benthic nutrient stock, much surpassing that represented by the phytoplankton. Growth in this biomass, and the magnitude of water-borne inputs, influenced the removals of Ca²⁺, K⁺ and inorganic N. The phytoplankton was probably limited by a low-P medium, to which co-precipitation of phosphate with CaCO₃ may have contributed. A vernal depletion of Si was probably limiting to diatom growth, and appeared to be mainly induced by benthic rather than planktonic diatoms. Examples of long-term change in composition of the phytoplankton and phytobenthos are noted and discussed in relation to the interaction of these components, nutrient enrichment, and possible alternative stable states.     

Interannual variation and climatic regulation of the CO2 emission from large boreal lakes

We studied the interannual variation of surface water partial pressure of CO₂ (pCO₂) and the CO₂ emissions from the 37 large Finnish lakes linking them to the water quality, catchment and climate attributes in 1996–2001. The lake water CO₂ was measured three times a year in the study lakes in 1998 and 1999 and for the rest of the years the CO₂ was modeled by measured alkalinity. The median annual CO₂ emission to the atmosphere ranged between 1.49 and 2.29 mol m^?2 a^?1. The annual CO₂ emission followed closely the annual precipitation pattern with the highest emission during the years when the precipitation was highest (r²=0.81–0.97, P<0.05). There was a strong negative correlation (r²=0.50–0.82, P<0.001) between O₂ and CO₂ saturation in the lake water during stratification suggesting effective decomposition of organic matter in the lakes. Furthermore, total phosphorus and the proportion of agricultural land in the catchment had significant positive correlations with CO₂ saturation.     

Development and application of a technique for estimating nutrient deficiency in soft sediments

A diffusion enrichment technique is presented which allows for chemical enrichment of soft surficial and shallow subsurface sediments and subsequent measurement of O₂ production. The sediment is enriched by inserting a perforated tube containing dialysis tubing filled with a nutrient/agar mixture. O₂ production by surficial sediment is measured using an inverted, translucent, polyethylene chamber over the sediment. The inside of the chamber contains a collapsible bag connected to the water outside the chamber. When water overlying the sediment is withdrawn from a sampling port, it is displaced with water from outside the chamber, thus preventing contamination of water samples with pore water from below. The technique was tested by enriching near-shore sediments in a large oligotrophic lake with inorganic N and P. NHinf4/^p+ additions significantly stimulated benthic primary production as measured by 0₂ production, whereas enrichment with POinf4/^3- had no effect.     

CALCIFICATION IN THE GREEN ALGA HALIMEDA. I. AN ULTRASTRUCTURE STUDY OF THALLUS DEVELOPMENT1

The ultrastructure of 4 species of the calcareous, siphonaceous alga Halimeda (H. cylindracea Decaisne, H. discoidea Decaisne, H. macroloba Decaisne and H. tuna (Ellis & Solander) Lamour) has been studied, and the observed changes during growth and development are related to changes in the degree of calcification. A distinct gradient in the types and quantities of cell organelles exists in a growing apical filament. As these filaments grow, branch, and eventually develop into a mature segment, changes in the organization of organelles such as mitochondria and chloroplasts are observed. Calcification begins when the chloroplasts reach structural maturity and when the peripheral utricles adhere (fuse). This adhesion of the peripheral utricles isolates the intercellular space (ICS) in which calcification occurs from the external seawater. Calcification begins in the outermost (pilose) cell wall layer of the walls facing into the ICS. The cell walls at the thallus exterior undergo extensive changes after utricular fusion; the pilose layer is lost, the cuticles of adjacent utricles fuse forming a ridge at their junction, and multiple cuticles are formed. The aragonite (CaCO₃) crystals which are initially precipitated within the pilose wall layer, rapidly increase in size and number, eventually filling much of the ICS. Only the initial nucleation of aragonite is associated with the pilose wall layer, the later precipitation of aragonite is totally independent of the pilose layer. In older segments secondary deposition of CaCO₃ also occurs around existing aragonite needles.     

ALGAL CALCIFICATION IN SOME CODIACEAE (CHLOROPHYTA): ULTRASTRUCTURE AND LOCATION OF SKELETAL DEPOSITS1,2

The capitular filaments of Penicillus and Rhipocephalus consist of an inner tube containing the cytoplasm and an outer calcified sheath. The sheath originates at the cell wall and differentiates into several layers which form the outer filament wall. CaCO₃ is deposited between organic layers within the sheath and is not in direct contact with the seawater. Pores within the sheath, usually uncalcified, may facilitate exchange of gases and solutes. The cytoplasm is characterized by vacuolar inclusions of calcium oxalate needles 50–150 μm long. A closed cortical surface is lacking. Udotea cyathiformis Dec. and U. conglutinata (Ellis & Sol.) Lam. are similar to Penicillus and Rhipocephalus, in addition showing some CaCO₃ between filaments (ICS-calcification). Udotea flabellum (Ellis & Sol.) Lam. is different as the filaments are profusely branched giving rise to a fully developed cortical surface. Pores and vacuolar calcium oxalate inclusions are absent. CaCO₃ deposition occurs within cortical filaments in between layers of the filament wall and subcortically in intercellular spares (ICS). Cortex calcification shows primary and secondary deposits bearing some resemblance to sheath calcification and to coralline red algae. In Rhipocephalus phoenix (Ellis & Sol.) Kütz., Penicillus pyriformis A. &E. Gepp, U. cyathiformis and U. conglutinata CaCO₃ is precipitated intracellularly within the sheath, in contrast to Halimeda and Cymopolia where it is deposited extracellularly in between filaments. U. flabellum takes an intermediate position showing both intra- and intercellular calcification. The sheath compartment volume is between 12.5 and 7500 μm³and 5–3 orders of magnitude smaller than the ICS-compartment. Compartment size and location of CaCO₃may bear on calcification mechanisms. One condition for such a mechanism may be restricted exchange of solutes (CO₂, CO₃^2-, HCO₃^-, O₂, Co²⁺). Codiaceae; filament ultrastructure; Penicillus; Rhipocephalus; Udotea     

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.     

Field detection of urease and carbonic anhydrase activity using rapid and economical tests to assess microbially induced carbonate precipitation

Microbial precipitation of calcium carbonate is a widespread environmental phenomenon that has diverse engineering applications, from building and soil restoration to carbon sequestration. Urease-mediated ureolysis and CO₂ (de)hydration by carbonic anhydrase (CA) are known for their potential to precipitate carbonate minerals, yet many environmental microbial community studies rely on marker gene or metagenomic approaches that are unable to determine in situ activity. Here, we developed fast and cost-effective tests for the field detection of urease and CA activity using pH-sensitive strips inside microcentrifuge tubes that change colour in response to the reaction products of urease (NH₃) and CA (CO₂). The urease assay proved sensitive and useful in the field to detect in situ activity in biofilms from a saline lake, a series of calcareous fens, and ferrous springs, finding relatively high urease activity in lake samples. Incubations of lake microbes with urea resulted in significantly higher CaCO₃ precipitation compared to incubations with a urease inhibitor, showing that the rapid assay indicated an on-site active metabolism potentially mediating carbonate precipitation. The CA assay, however, showed less sensitivity compared to the urease test. While its sensitivity limits its utility, the assay may still be useful as a preliminary indicator given the paucity of other means for detecting CA activity in the field. Field urease, and potentially CA, activity assays complement molecular approaches and facilitate the search for carbonate-precipitating microbes and their in situ activity, which could be applied toward agriculture, engineering and carbon sequestration technologies.     

β-Poly(l-malate) production by Physarum polycephalum

β-Poly(l-malate) (PMLA) production in Physarum polycephalum has been followed by using d-[1-¹³C]glucose and Ca¹³CO₃. Nuclear magnetic resonance studies of PMLA showed that the ¹³C label from [1-¹³C]glucose was incorporated in the presence of CaCO₃ into positions C-3 (-CH₂-) and C-4 (-CO-) of the l-malate repeating unit of PMLA. The ¹³C label from Ca¹³CO₃ was incorporated into position C-4 and indicated that not only the endogenous CO₂ but also the exogenous CO₂ from CaCO₃ served significantly as a carbon source for PMLA production. In the absence of CaCO₃, the ¹³C labeling pattern of PMLA from d-[1-¹³C]glucose was almost indistinguishable from that for the natural abundance ¹³C-NMR spectrum of the polymer. These results indicated that l-malate used for PMLA production is synthesized either via carboxylation of pyruvate and reduction of oxaloacetate in the presence of CaCO₃ or via the oxidative tricarboxylic acid (TCA) cycle in the absence of CaCO₃. Avidin strongly inhibited the formation of l-malate via carboxylation; the ¹³C labeling pattern of PMLA in the presence of CaCO₃ was almost identical with that for the natural abundance spectrum when avidin was added, indicating that l-malate utilized for PMLA production was supplied under this condition by the oxidative TCA cycle. Received: 16 March 1999 / Received revision: 5 May 1999 / Accepted: 7 May 1999     

Effects of temperature and sediment properties on benthic CO2 production in an oligotrophic boreal lake

1. Temperature and many other physical and chemical factors affecting CO₂ production in lake sediments vary significantly both seasonally and spatially. The effects of temperature and sediment properties on benthic CO₂ production were studied in in situ and in vitro experiments in the boreal oligotrophic Lake Pääjärvi, southern Finland. 2. In in situ experiments, temperature of the water overlying the shallow littoral sediment varied seasonally between 0.5 and 15.7 °C, but in deep water (≥20 m) the range was only 1.1–6.6 °C. The same exponential model (r² = 0.70) described the temperature dependence at 1.2, 10 and 20 m depths. At 2.5 and 5 m depths, however, the slopes of the two regression models (r² = 0.94) were identical but the intercept values were different. Sediment properties (wet, dry, mineral and organic mass) varied seasonally and with depth, but they did not explain a significantly larger proportion of variation in the CO₂ output rate than temperature. 3. In in vitro experiments, there was a clear and uniform exponential dependence of CO₂ production on temperature, with a 2.7‐fold increase per 10 °C temperature rise. The temperature response (slope of regression) was always the same, but the basic value of CO₂ production (intercept) varied, indicating that other factors also contributed to the benthic CO₂ output rate. 4. The annual CO₂ production of the sediment in Lake Pääjärvi averaged 62 g CO₂ m^?2, the shallow littoral at 0–3 m depth releasing 114 g CO₂ m^?2 and deep profundal (>15 m) 30 g CO₂ m^?2. On the whole lake basis, the shallow littoral at 0–3 m depth accounted for 53% and the sediment area in contact with the summer epilimnion (down to a depth c. 10 m) 75% of the estimated total annual CO₂ output of the lake sediment, respectively. Of the annual production, 83% was released during the spring and summer. 5. Using the temperature‐CO₂ production equations and climate change scenarios we estimated that climatic warming might increase littoral benthic CO₂ production in summer by nearly 30% from the period 1961–90 to the period 2071–2100.     

Chemisty of lake water and groundwater in areas of contrasting glacial drifts in Eastern Minnesota

The water chemistry of 28 lakes from both sides of the border between glacial drifts of the Grantsburg lobe (high CaC0₃) and Superior lobe (low CaCO₃) in east-central Minnesota was examined to determine if drift type influences lake-water chemistry. Similar analyses were performed on groundwater samples taken from wells near each lake. Concentrations of Ca⁺⁺, Mg⁺⁺, HC0 _inf3 ^sup- , SO _inf4 ^sup- were significantly higher in lakes of the Grantsburg lobe, whereas K+, Si0₂, and HCO ₃ ^- were significantly higher in samples of groundwater from the Grantsburg lobe. There was no correlation between groundwater concentrations of particular ions and lake-water concentrations of the same ions, implying that the sources of dissolved ions in lake water are shallow groundwater and soil leachates rather than the deeper groundwater sampled here. Na⁺ and Cl^- concentrations in some lakes appear to be strongly influenced by the use of de-icing salt on highways in winter rather than by differences in drift lithology.Limnological Research Center, University of Minnesota     

A nonlinear calcification response to CO2-induced ocean acidification by the coral Oculina arbuscula

Anthropogenic elevation of atmospheric pCO₂ is predicted to cause the pH of surface seawater to decline by 0.3–0.4 units by 2100 AD, causing a 50% reduction in seawater [CO₃ ²⁻] and undersaturation with respect to aragonite in high-latitude surface waters. We investigated the impact of CO₂-induced ocean acidification on the temperate scleractinian coral Oculina arbuscula by rearing colonies for 60 days in experimental seawaters bubbled with air-CO₂ gas mixtures of 409, 606, 903, and 2,856 ppm pCO₂, yielding average aragonite saturation states (Ω_A) of 2.6, 2.3, 1.6, and 0.8. Measurement of calcification (via buoyant weighing) and linear extension (relative to a ¹³⁷Ba/¹³⁸Ba spike) revealed that skeletal accretion was only minimally impaired by reductions in Ω_A from 2.6 to 1.6, although major reductions were observed at 0.8 (undersaturation). Notably, the corals continued accreting new skeletal material even in undersaturated conditions, although at reduced rates. Correlation between rates of linear extension and calcification suggests that reduced calcification under Ω_A = 0.8 resulted from reduced aragonite accretion, rather than from localized dissolution. Accretion of pure aragonite under each Ω_A discounts the possibility that these corals will begin producing calcite, a less soluble form of CaCO₃, as the oceans acidify. The corals’ nonlinear response to reduced Ω_A and their ability to accrete new skeletal material in undersaturated conditions suggest that they strongly control the biomineralization process. However, our data suggest that a threshold seawater [CO₃ ²⁻] exists, below which calcification within this species (and possibly others) becomes impaired. Indeed, the strong negative response of O. arbuscula to Ω_A = 0.8 indicates that their response to future pCO₂-induced ocean acidification could be both abrupt and severe once the critical Ω_A is reached.     

The relative contributions of biological and abiotic processes to carbon dynamics in subarctic sea ice

Knowledge on the relative effects of biological activity and precipitation/dissolution of calcium carbonate (CaCO₃) in influencing the air-ice CO₂ exchange in sea-ice-covered season is currently lacking. Furthermore, the spatial and temporal occurrence of CaCO₃ and other biogeochemical parameters in sea ice are still not well described. Here we investigated autotrophic and heterotrophic activity as well as the precipitation/dissolution of CaCO₃ in subarctic sea ice in South West Greenland. Integrated over the entire ice season (71 days), the sea ice was net autotrophic with a net carbon fixation of 56 mg C m^?2, derived from a sea-ice-related gross primary production of 153 mg C m^?2 and a bacterial carbon demand of 97 mg C m^?2. Primary production contributed only marginally to the TCO₂ depletion of the sea ice (7–25 %), which was mainly controlled by physical export by brine drainage and CaCO₃ precipitation. The net biological production could only explain 4 % of this sea-ice-driven CO₂ uptake. Abiotic processes contributed to an air-sea CO₂ uptake of 1.5 mmol m^?2 sea ice day^?1, and dissolution of CaCO₃ increased the air-sea CO₂ uptake by 36 % compared to a theoretical estimate of melting CaCO₃-free sea ice. There was a considerable spatial and temporal variability of CaCO₃ and the other biogeochemical parameters measured (dissolved organic and inorganic nutrients).     

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.     

Diel, episodic and seasonal changes in pH and concentrations of inorganic carbon in a productive lake

• 1 Two pH electrodes and a thermistor were used to record conditions in the surface of Esthwaite Water every 15 min over a 12-month period. Combined with approximately weekly measurements of alkalinity they allowed inorganic carbon speciation to be calculated.
• 2 Large changes in pH from 7.1 to nearly 10.3, and hence in concentrations of inorganic carbon species, were measured over a year. Carbon speciation and pH varied on a diel, episodic and seasonal basis. Diel variation of up to pH 1.8 was recorded, although typical daily variation was between 0.03 and 1.06 (5 and 95 percentiles). Daily change in concentration of inorganic carbon varied between 4 and 63 mmol m^-3 (5 and 95 percentiles).
• 3 During lake stratification, episodes of high pH, typically of 1–2 weeks' duration were interspersed with episodes of lower pH. These changes appeared to relate to the weather: e.g. low wind velocity, high pressure, low rainfall and high sunshine hours correlated with periods of high pH.
• 4 Seasonal progression of carbon depletion generally followed stratification and the development of high phytoplankton biomass. When the lake was isothermal, the phytoplankton biomass caused relatively small amounts of carbon depletion.
• 5 During autumn, winter and spring, the lake had concentrations of CO₂* (free CO₂) up to 0.12 mol m^-3 which is nearly seven times the calculated atmospheric equilibrium concentration so the lake will accordingly be losing carbon to the atmosphere. In contrast, during periods of elevated pH the concentration of CO₂* was reduced close to zero and the lake will take up atmospheric CO₂. The rates of transfer between water and the atmosphere were estimated using a chemical equilibrium model with three boundary layer thicknesses. The calculations show that over a year the lake loses CO₂ to the atmosphere with the current mean atmospheric level of 360 μmol mol^-1, at between 0.28 and 2.80 mol m^-2 yr^-1. During elevated pH, rates of CO₂-influx increased up to nearly tenfold as a result of chemical-enhancement by parallel flux of HCO^-₃. Input of CO₂* to the lake from the catchment is suggested to be the main source of the carbon lost to the atmosphere.
• 6 The turnover time for CO₂ between the air and water was calculated to be 1 year for the gross influx and 3.3 years for the net flux. These values are less than the average water residence time of 0.25 years, which indicates that over a year inflow from streams is a more important source of inorganic carbon than the atmosphere.
• 7 Influx of CO₂ from the atmosphere was calculated to be roughly equivalent to between 1 and 4% of the rates of production in the water during mid-summer indicating that this source of inorganic carbon is not a major one in this lake.
• 8 Influx of CO₂ from the hypolimnion was estimated on one occasion to be 6.9 10^-9 mol m^-2 s^-1 using transfer values based on mass eddy-diffusion. These rates are equivalent to 23% of the rate of influx of CO₂ from the atmosphere on this occasion which suggests that the hypolimnion is probably a small source of inorganic carbon to the epilimnion. The exception appears to be during windy episodes when pH is depressed. Calculations based on depth-profiles of CO₂* and HCO^-₃ suggest that the measured changes in pH can be accounted for by entrainment of hypolimnetic water into the epilimnion.
• 9 The solubility product for calcite was exceeded by up to about sixfold which, although insufficient to allow homogeneous precipitation, may have allowed heterogeneous precipitation around algal particles.

     

Aragonite and calcite cementation in “boulder-controlled” meteoric environments on the Fern Pass rockslide (Austria): implications for radiometric age dating of catastrophic mass movements

On the Fern Pass rockslide (Eastern Alps, Austria), projecting boulders collected surface runoff and delayed percolation of water into the rockslide mass, leading to decimetre-scale, fluctuating, phreatic/vadose diagenetic systems along their contact. In these systems, aragonite and calcite precipitation were nourished mainly by dissolution of carbonate-rock flour. Cement precipitation was limited to southern- and eastern-exposed “runoff haloes” of boulders and mainly resulted in cemented breccias. Aragonite precipitation was related to dissolved Mg²⁺ and/or to high CaCO₃ supersaturation in evaporative-concentrated pore waters. Early aragonite cement yielded a ²³⁴U/²³⁰Th age of 4,150 ± 100 years. Relative to other radiometric ages (³⁶Cl, ¹⁴C; by other authors) for the rockslide event, the U–Th age of the aragonite is the most precise proxy of depositional age. Carbonate cements are present in other rockslide and rockfall deposits also. U–Th dating of such cements is thus a comparatively rapid and inexpensive method of minimum-age dating catastrophic mass movements.     

Chemical and isotopic composition of karstic lakes in Jamaica,West Indies

Lakes in the limestone region of Jamaica exhibit a range of chemical characteristics that reflect varying inputs from precipitation, surface runoff and groundwater, together with the subsequent evolution of the water within the limnic environment. Detailed spatial and temporal sampling was conducted on one lake, Wallywash Great Pond. Chemical data, together with D/H, ¹⁸O/¹⁶O, ¹³C/¹²C and ⁸⁷Sr/⁸⁶Sr ratios confirm that the karstic spring waters entering the lake evolve chemically through degassing, mixing with rainfall and runoff, biogenic decalcification (resulting mainly from bicarbonate assimilation by the high biomass of submerged macrophytes), and evaporation. Modern carbonate sedimentation in Wallywash Great Pond is largely of high-Mg calcite. This is consistent with Mg/Ca molar ratios >2 within much of the lake. However, aragonite forms on the adaxial leaf surfaces of Potamogeton spp. This may be explained either as a result of locally elevated Mg concentrations or a high degree of supersaturation favouring very rapid carbonate precipitation. Two small lakes to the north of Wallywash Great Pond show minor influence of the Na-Cl dominated coastal aquifer, suggesting that coastal lakes are sensitive to variations in the boundary between fresh and brackish groundwater caused by changes in climate or sea level. Their ¹³C/¹²C ratios are strongly influenced by biogenic CO₂ derived from plant respiration or decay.