Mathematical modeling of PCB bioaccumulation in Perna viridis

In the present work, we built a mathematical model of polychlorinated biphenyl (PCB) bioaccumulation in Perna viridis, namely, a one-compartment model with a time dependent incorporation rate R (μg g⁻¹ lipid per ppb water per day), with positive substrate cooperativity as the underlying physical mechanism. The temporal change of the PCB concentration Q (μg g⁻¹ lipid) in the soft tissues of the mussel depends on the competition of the input rate RW and the output rate kQ, where W is the concentration of PCB in water (ppb water) and k is the elimination rate (per day). From our experimental data, k=0.181±0.017 d⁻¹. The critical concentration in water W_c for positive substrate cooperativity was found to be 2.4 ppb. Below W_c, R is a constant. For a water concentration of 0.5 ppb Aroclor 1254, R=24.0±2.4 μg g⁻¹ lipid ppb⁻¹ d⁻¹. Above W_c, positive substrate cooperativity comes into effect and R becomes a function of time and dependent on the concentration Q in a form R=γQ/(Q+δ). This is the case for a water concentration of 5 ppb Aroclor 1254, where γ=15.1 μg g⁻¹ lipid ppb⁻¹ d¹ and δ≈200 μg g⁻¹ lipid. From this model, the uptake is exponentially increasing when the PCB concentration in the mussel is small compared to 200 μg g⁻¹ lipid, and hyperbolically increasing when the concentration is large compared to 200 μg g⁻¹ lipid, which are consistent with the experimental data. The model is useful for understanding the true processes taking place during the bioaccumulation and for risk assessment with higher confidence. Future experimental data which challenge the present model are anticipated and in fact desirable for improvement and perfection of the model.     

Heavy metals in surface sediment and epibenthic macroinvertebrates from the coastal zone and continental slope of Kenya

In surface sediments, a statistically significant increase was measured in the concentration of copper and cadmium along all transects, and of zinc along only the most southern (Gazi) transect, radiating into the Indian Ocean perpendicular to the Kenyan coast. Mean copper and cadmium increased from 5 to 30 μg g⁻¹ dry wt and from 0.01 to 0.34 μg g⁻¹ dry wt in shallow coastal (±20 m depth) to deep-sea stations (±2000 m depth), respectively. These gradients were found both during the south-east monsoon and north-east monsoon period. The shallow estuarine zone of the Sabaki river mouth showed significantly enhanced levels of total organic carbon and nitrogen and all metals analysed, except cadmium.In crustaceans, the concentration of copper and particularly cadmium was significantly above baseline levels, varying from 45 to 90 μg g⁻¹ dry wt and 1.0 to 8.5 μg g⁻¹ dry wt, respectively. Zinc levels (49–102 μg g⁻¹ dry wt) were at about baseline levels or a little elevated. On the contrary, lead showed very low concentrations, varying from 0.1 to 0.6 μg g⁻¹ dry wt. Other species generally showed the same pattern.     

Effects of 4-nonylphenol exposure in mussels (Mytilus galloprovincialis) and crabs (Carcinus aestuarii) with particular emphasis on vitellogenin induction

Since it is often difficult to estimate possible adverse effects due to contamination in selected ecosystems, multi-species biomonitoring may provide more information, taking into account different routes of exposure, ecological roles and metabolic capabilities of animals. In this context, we exposed for 7 days the mussel Mytilus galloprovincialis and the crab Carcinus aestuarii to 4-nonylphenol (NP), a well-known xenoestrogen. In mussels (0–0.2 mg NP l⁻¹), we measured NP bioaccumulation in soft tissues and vitellogenin (Vg)-like protein levels in digestive glands from both males and females by the alkali-labile phosphate assay (ALP). As no reference data were available for crab exposure, the NP 96-h LC₅₀ value was previously determined. Then, in sublethally exposed (0–1.0 mg NP l⁻¹) male crabs, NP bioaccumulation and Vg levels were measured in hemolymph, gonads and digestive gland. Bioaccumulation of NP increased from 43 to 371 μg g⁻¹ d.w. in mussels, and from 3.6 to 37 μg g⁻¹ d.w. in crabs, depending on the NP concentration in water. Dose-dependent Vg-like protein induction was observed in both species, appearing to be related to NP bioaccumulation, although a partial decrease was recorded at the highest concentration tested. A similar trend was observed in both digestive gland and gonad of exposed crabs; Vg increased to a lesser extent, although significantly, in hemolymph. Results demonstrated that NP induces Vg synthesis both in male and female mussels, as well as in male crabs. On the basis of the responsiveness of both species investigated, a multi-species approach is indicated in biomonitoring programmes.     

Conductivity as a predictor of a total cations and salinity in Ethiopian lakes and rivers: revisiting earlier models

We used regression analyses of water samples from 18 lakes, nine rivers, and one spring in Ethiopia to (a) test the hypothesis that water bodies of relatively higher salinity (K₂₅>1000 μS cm⁻¹) have a different conductivity to salinity relationship than waters of lower salinity (K₂₅ < 1000 μS cm⁻¹), and (b) develop models to predict total cations and salinity from conductivity that can be used for Ethiopian waters and other African aquatic systems of similar chemical composition. We found no statistical difference in the bilogarithmic relationships (total cations vs. conductivity; salinity vs. conductivity) for waters of higher salinity (K₂₅ > 1000 μS cm⁻¹) and waters of lower salinity (K₂₅ < 1000 μS cm⁻¹). However, comparison among our models and models from the literature suggests that developing separate equations for low and high salinity water bodies has some merit. We believe that the equations developed in this study can be used for Ethiopian waters and other African waters within the range of conductivity in this study.     

Lake Koronia, Greece: Shift from autotrophy to heterotrophy with cultural eutrophication and progressive water-level reduction

Lake Koronia, a Ramsar site, is shallow, polymictic, hypertrophic and until recently was aerially the fourth largest lake in Greece. Although exceeding 5 m in the past, lake depth has declined progressively from 3.8 m in 1980 to < 1 m in 1997, reducing surface area and water volume by 50% and 80%, respectively. Specific conductivityincreased from 1300 μS cm⁻¹ in 1977 to >6000 μS cm⁻¹ in 1991. Increased phosphate concentrations from the late 1970's (8–45 μg L⁻¹) to the late 1990's (100–1000 μg L⁻¹) document that the previously eutrophic system with a limited littoral zone switched to hypertrophy dominated by massive cyanobacteria blooms. Oxygen saturation of the water column increased progressively from about 80% in 1983 to full saturation about 1993, after which it decreased progressively to only 20% saturation in 1997. In spite of cyanobacteria dominance, community metabolism of the lake switched from progressively increasing autotrophy to rapidly advancing heterotrophy associated with progressive water-level reduction leading to fish extirpation in the lake.     

Surface energy balance at a tropical station

Summary Studies of various fluxes, namely net radiation, soil heat, sensible heat and latent heat observed at a tropical station are presented in this paper. The time variation of these fluxes are examined in relation to various meteorological parameters and atmospheric conditions. The turbulent transfer coefficients have been evaluated to examine the applicability of the classical theory or the non-equivalence theory for eddy transport in the lower layers of the atmosphere. The energy balance at a tropical station is evaluated. It is found over year there is a net surplus of 94,000 ly. A detailed discussion of the disposal of this energy by various consuming processes is given.Symbols and notation All the quantities represented by symbols in the text of the paper are defined below C _p specific heat at constant pressure in cal. g^–1 °K - E evaporation in g cm^–2 hr^–1 - E ^* evaporative heat flux cal. cm^–2 sec^–1 (in Eq. 10) - e vapour pressure in millibars - e _z ,e _2z vapour pressure at heightsz and 2z - g acceleration due to gravity - H sensible heat flux cal cm^–2 sec^–1 (in Eq. 12) - K _M ,K _H ,K _W coefficients of eddy diffusivities of momentum, heat, and water vapour respectively in cm² sec^–1 - k von Karman' constant=0.4 - L Monin-Obukhov length (according to Monin and Obukhov [53] the structure of the turbulent boundary layer is determined by the non-dimensional variableZ/L whereL is defined byL=–(u _* ³ C _p T)/(kgH) - ly langleys - Q _c Q—sensible heat flux in langleys (in Eqs. 3 and 4) - Q _e E—latent heat flux in langleys (in Eqs. 3 and 4) - Q _s S—soil heat flux in langleys (in Eqs. 3 and 4) - Q _i Q _c +Q _e +Q _s whenK _M K _H K _W , (in Eq. 6) - Q' _i Q' _c +Q' _e +Q _s whenK _M =K _H =K _W (in Eq. 7) - qq mean specific humidity g kg^–1     

Neodymium isotopic study of Baffin Bay water: sources of REE from very old terranes

Water samples were collected from Baffin Bay and surrounding areas in order to evaluate this region as a potential source of Nd from old continental material to Atlantic water. The isotopic data ranged from ε_Nd(0) = −9.0 to −26 with most of the data around ε_Nd(0) = −20 compared with values of North Atlantic Deep Water (NADW) with ε_Nd(0) = −13.5. The concentration of Nd in Baffin Bay waters was as high as 6 × 10⁻¹² g/g compared with 2.5 × 10⁻¹² g/g for NADW. The combination of low ε_Nd and high Nd concentration indicates that Baffin Bay may be a significant source of Nd from very old crustal material. A simple box model was used to evaluate the contribution to the Nd budget of NADW and it was concluded that a substantial fraction of the Nd from ancient crustal sources that is required to maintain the isotopic composition of NADW could be supplied by Baffin Bay outflow.     

Microcosm experiments on the effect of nutrient enrichment and a soil layer on the development of freshwater plankton

We investigated the response of phytoplankton and zooplankton to experimental alteration of nitrate and phosphate levels in outdoor enclosures. Experiments were conducted in summer and winter and in the absence and presence of a layer of soil. The tubs (12 in all) except the two plain water controls were manured initially with a mixture of fresh cowdung (50g 1⁻¹), mustard oil cake (25 g l⁻¹) and poultry wastes (25 g l⁻¹; mostly excreta), prior to enrichment. Water samples were collected from the experimental tubs twice a week to measure selected physico-chemical and biological variables. Water temperature in the summer experiments ranged from 20–30 °C and during the winter experiments from 11–15 °C. The pH values ranged from 8.0 to 9.5 and the dissolved oxygen levels from 8.2–10.0 mg l⁻¹. The levels of soluble reactive phosphorus and nitrate nitrogen ranged from undetectable levels to 1800 μg l⁻¹ and 6000 μg l⁻¹, respectively. The increase in chlorophyll-a following enrichment was rapid (3–7 days) during summer, but slower in winter (7–14 days). The predominant phytoplankton species observed in the tubs belong to the genera Sphaerocystis, Chlorella, Scenedesmus, Cosmarium, Ulothrix, Zygnema, Gonium and Pandorina. The rotifer species observed were Brachionus calyciflorus, Rotaria neptunia, Lecane bulla, L. luna, L. unguitata, Euchlanis dilatata, Asplanchna intermedia, Pseudoharringia spp., Eosphora spp., Lepadella ovalis, Epiphanes brachionus, Hexarthra mira and Cephalodella gibba. The cladocerans observed were Macrothrix spp. and Alona spp.     

Ecosystem water use efficiency in an irrigated cropland in the North China Plain

The eddy covariance technique and the cuvette method were used to investigate water use efficiency in an irrigated winter wheat (Triticum asetivum L.)/summer maize (Zea mays L.) rotation system in the North China Plain. The results show that ecosystem water use efficiency (WUE_e) changed diurnally and seasonally. Daily maximal WUE_e appeared in the morning. WUE_e generally peaked in late April in wheat field and in late July/early August in maize field. From 2003 to 2006, seasonal mean WUE_e was 6.7–7.4 mg CO₂ g⁻¹ H₂O for wheat and 8.4–12.1 mg CO₂ g⁻¹ H₂O for maize. WUE_e was much lower than canopy water use efficiency (WUE_c) under small leaf area index (LAI) but very close to WUE_c under large LAI. With the increase in LAI, WUE_e enlarged rapidly under low LAI but slowly when LAI was higher than one. WUE_e was greater on the cloudy days than on the sunny days. Under the same solar radiation, WUE_e was higher in the morning than in the afternoon. The ratio of internal to ambient CO₂ partial pressure (C_i/C_a) decreased significantly with the increase in photosynthetically active radiation (PAR) when PAR was lower than the critical values (around 500 and 1000 μmol m⁻² s⁻¹ for wheat and maize, respectively). Beyond critical PAR, C_i/C_a was approximately constant at 0.69 for wheat and 0.42 for maize. Therefore, when LAI and solar radiation was large enough, WUE_e has negative correlation with vapor pressure deficit in both of irrigated wheat and maize fields.     

Respiratory adaptations to oxygen lack in three species of Glossiphoniidae (Hirudinea) in Lake Esrom, Denmark

The weight-specific respiration rate (μl O₂ mg⁻¹ AFDW h⁻¹) of three species of leech from Lake Esrom, Denmark, Glossiphonia concolor, G. complanata and Helobdella stagnalis was measured in a closed stirred chamber with a micro electrode. At declining oxygen concentration (mg O₂ l⁻¹) all three species expressed moderate ability to regulate respiration, in G. concolor and G. complanata down to 2 mg O₂ l⁻¹, in H. stagnalis down to 0.75 mg O₂ l⁻¹. Survival in anoxia was measured in closed bottles. The time to 50% survival (LD₅₀) was 30 days in G. concolor at 20 °C and 30 and 4 days in H. stagnalis at 10 and 20 °C, respectively. The results were discussed in relation to habitat and spatial distribution of the three species in the lake.     

A hydrobiological study to interpret the presence of desmids in Lake Zirahuén, México

Monthly collections of phytoplankton were supported by physical–chemical data and measures of chlorophyll a concentrations in the search for particular environmental factors that could explain the constant presence of desmids in a Mexican tropical lake, a characteristic not common among the phytoplanktic communities of Mexican lakes. Samplings were taken from the water column in the deepest part of the lake (40 m) and intensified in the metalimnetic zone, whose establishment was monitored by observations of temperature and oxygen profiles. The general behavior of Lake Zirahuén was typical of warm monomictic tropical lakes at high elevation: a short mixing phase during the hemispheric winter. The depth of Z_MIX and Z_eu revealed a well-illuminated epilimnion, suggesting that phytoplankton communities are not likely to be light-limited. The oligotrophic nature of the lake is indicated by discrete concentrations of inorganic nutrients, P_TOT in the interval of 0.01–0.03 mg l⁻¹ and chlorophyll a between 0.23 and 3.98 μg l⁻¹. These characteristics together with a low concentration of calcium, define a lacustrine environment different from other Mexican lakes, and one that could be suitable for desmids communities.     

Coupling of early diagenetic processes and sedimentary dynamics in tropical shelf environments: the Gulf of Papua deltaic complex

Tropical mobile mud belts represent a major class of biogeochemical and diagenetic systems characterized by extensive and frequent physical reworking of fine-grained, organic-rich deposits underlying oxygenated waters. Large regions of the Gulf of Papua, Papua New Guinea deltaic complex are dominated by such conditions. A reworked mud belt lies within the inner shelf between 10 and 20 m depth on a sedimentary clinoform derived from coalescing deltas. Deposits across the topset are typically suboxic, nonsulfidic over the upper 0.5–1 m, and have low to moderate maximum pore water concentrations of dissolved Fe(II) and Mn(II) (100–200, but up to 800 μM). Sediments are reactive, with surficial ΣCO₂ production 0.1–0.3 mM d⁻¹ and benthic O₂ fluxes 23±15 mmol m⁻² d⁻¹ (upper 20 cm). The highest rates occur within inner topset deposits (10–20 m) and near the high accumulation rollover region of the topset–foreset beds (40–50 m). Lower rates are found inshore along intertidal channels—mangrove fringe and within scoured or exposed consolidated deposits of the middle topset region. Remineralization rate patterns are independent of relative dominance by terrestrial or marine carbon in sediments. Dissolved O₂ usually penetrates 2–5 mm into surface sediments when macrofaunal burrows are absent. More than 75% of the highly reactive sedimentary Fe(III) pool (350–400 μmol g⁻¹) is typically diagenetically reduced in the upper 0.5 m. Pore water can be measureably depleted at depths >0.5 m, but dissolved H₂S generally remains below detection over the upper 1–2 m. As in other deltaic topset regions, concentration gradients often indicate that compared to many marine deposits of similar sediment accumulation rates, relatively refractory C_org is supplied to the SO₄ reducing zone. Sedimentary C/S ratios are 4–6 within the suboxic topset regions but decrease to <3 in offshore foreset beds where sulfidic diagenesis dominates. Only 15–20% of the diagenetically reduced Fe(II) is pyritic and a maximum of 10–25% is carbonate, implying that most Fe(II) is associated with authigenic or lithogenic silicates or oxides. The dominance of suboxic, nonsulfidic diagenetic processes reflect coupling between delivery of oxide-rich terrestrial debris, remobilization and reoxidation of deposits, and repetitive entrainment/remineralization of both labile and refractory organics. Distinct sedimentary indicators of reactive, suboxic mobile mud belts within tropical climatic zones are: abundant total highly reactive Fe (ΣFeR )>300 μmol g⁻¹; most reactive Fe is diagenetically reduced (ΣFe(II)/ΣFeR0.7–0.8); the proportion of diagenetically reduced Fe present as pyrite is low (Py–Fe(II)<0.2); C/S 4–8; and C_org/particle surface area <0.4 (mg C m⁻²). These depositional environments must be most common in tropical climates during high sea stand.     

Changes in the yield of chlorophyll a from dissolved available inorganic nitrogen after an enrichment event—applications for predicting eutrophication in coastal waters

An understanding of the dynamic relationship between nitrogen supply and the formation of phytoplankton biomass is important in predicting and avoiding marine eutrophication. This relationship can be expressed as the short-term yield q of chlorophyll from dissolved available inorganic nitrogen (DAIN), the sum of nitrate, nitrite and ammonium. This paper communicates the results of a continuous culture nitrate enrichment experiment undertaken to investigate the cumulative yield of chlorophyll from DAIN (q). The purposes of the study were: to acquire a better understanding of the relationship between chlorophyll formation and DAIN; to obtain values that could be used in models for predicting eutrophication. The results of a time series experiment carried out using microplankton (all organisms <200 μm in size) indicate that the parameter q does not have a single value but is affected by the ecophysiological response of phytoplankton to changing nutrient status after an enrichment event. It is also dependent on changes in the allocation of nitrogen between autotrophs and heterotrophs. The value of yield obtained at the height of the bloom can be represented by q (max) (2.35 μg chl (μmol N)⁻¹). The post-bloom, steady state value of q can be represented by q_eq (0.95 μg chl (μmol N)⁻¹). The microcosm steady state yield was not significantly different from the median value obtained from synoptic studies of Scottish west coast waters. It is proposed that q_eq is the most appropriate value for assessing the general potential for eutrophication resulting from continuous nutrient enrichment into coastal waters. It is further proposed that q (max) be used for cases of sporadic enrichment and where a short burst of unrestricted growth may be detrimental.     

The high content of polyunsaturated fatty acids in Nannochloropsis limnetica (Eustigmatophyceae) and its implication for food web interactions, freshwater aquaculture and biotechnology

In the eustigmatophycean Nannochloropsis limnetica the content of polyunsaturated fatty acids (PUFA) is extremely high in comparison to different planktonic green algal taxa in freshwater ecosystems. The sums of n-6 and n-3 fatty acids in N. limnetica were ten-fold higher than in the other picoplankton Choricystis minor and Pseudodictyosphaerium jurisii, and higher than in the nanoplanktonic green algae Chlorella vulgaris, Monoraphidium neglectum and Scenedesmus obtusiusculus. The content of fatty acids in N. limnetica was highly variable under different culture conditions. The highest concentrations of PUFA in N. limnetica were found in non-aerated suspension cultures, with a high content of phosphate (40 mg l⁻¹ K₂HPO₄) in the culture medium: linoleic acid 22.19 mg g⁻¹ DW, arachidonic acid 10.52 mg g⁻¹ DW, and eicosapentaenoic acid 55.56 mg g⁻¹ DW. N. limnetica represent a high-quality food resource in freshwater food chains. Furthermore, cultures of this eustigmatophycean alga have a high potential for use in biotechnology and aquaculture.     

Hemolytic activity and fatty acids composition in the ichthyotoxic dinoflagellate Cochlodinium polykrikoides isolated from Bahía de La Paz, Gulf of California

The hemolytic activity of the dinoflagellate Cochlodinium polykrikoides from Bahía de La Paz, Gulf of California was investigated as part of the ichthyotoxic mechanism of this microalga. Two different kinds of erythrocytes, fish and human, were tested for the hemolytic assay. Since fatty acids have been associated with hemolytic activity in C. polykrikoides, the composition of fatty acids of this dinoflagellate was also analyzed. The concentration of C. polykrikoides causing 50% hemolysis (HE₅₀) was 4.88 and 5.27 × 10⁶ cells L⁻¹, for fish and human erythrocytes, respectively. According to the standard curve of saponin, an equivalence between the hemolytic activity of saponin and the dinoflagellate concentration was found with 1 μg saponin mL⁻¹ equivalent to 1 × 10⁶ cells L⁻¹ of C. polykrikoides. The polyunsaturated fatty acids: hexadecaenoic (16:0), docosahexaenoic (22:6 n3) and octadecapentaenoic (18:5 n3) were found in an abundance of 62% of total fatty acids.     

Distribution of dissolved free amino acids, dissolved inorganic nitrogen and chlorophyll a in the surface microlayer and subsurface water of the Yellow Sea, China

Concentrations of 14 different dissolved free amino acids (DFAA), dissolved inorganic nitrogen (DIN), and chlorophyll a were determined in the surface microlayer and subsurface waters at 41 stations in the Yellow Sea, China in April 2006. The concentrations of DFAA in the subsurface water ranged from 0.13 to 1.62 μM, with an average of 0.57±0.05 μM, while those in the surface microlayer varied between 0.22 and 2.6 μM, with an average of 0.94±0.08 μM. Major constituents of DFAA present in the study area were glycine, alanine, glutamic acid, serine and histidine. One-way analysis of variance (ANOVA) showed no significant difference in average mol fractions of DFAA between microlayer and subsurface water (F=0.0440, P=0.8355). Hierarchical cluster analysis of the station similarity based on the DFAA composition in both the surface microlayer and subsurface water separated three clusters of stations at the 70% Bray–Curtis similarity level. The average concentrations of chlorophyll a and DIN were 1.18 (0.34–4.44) μg L⁻¹ and 16.57 (3.98–49.59) μM in the subsurface water, and those in the surface microlayer were 1.30 (0.24–3.97) μg L⁻¹ and 18.56 (5.77–48.93) μM, respectively. Our results showed that concentrations of chlorophyll a (r²=0.7940, n=41, p<0.0001), DIN (r²=0.6939, n=41, p<0.0001) and DFAA (r²=0.2416, n=41, P=0.0011) in the microlayer were, respectively, correlated with their subsurface water concentrations, implying that there was a strong exchange effect between the microlayer and subsurface water. The enrichment factor of DFAA in the microlayer ranged from 0.47 to 2.24 with a mean of 1.88±0.16.     

Effective barometric admittance and gravity residuals

In the analysis of surface gravity signals that may originate from the Earth's core, the step of correcting for the atmospheric pressure fluctuations is one that must be done carefully. We apply two techniques for determining the local, or effective, barometric admittance function between simultaneous observations of surface gravity and pressure. The first is a frequency domain fit that computes the admittance on a band-by-band basis. Using data from both the Canadian and French superconducting gravimeters we determined that the magnitude of the local, or background, admittance increases smoothly and monotonically from about 0.2 μgal mbar⁻¹ at long periods (> 10 days) to about 0.35 μgal mbar⁻¹ at frequencies greater than 3 cycles per day (c.p.d.); the phase lag is within a few degrees of 180°. By comparison, the effective admittances of the large-scale harmonics of the solar heating tide (S₁---S₇) are much smaller, between 0.1 and 0.3 μgal mbar⁻¹, for most of the harmonics of a day. In the second approach we fit a symmetrical time domain admittance function having lengths between 1 and 19 h using both a standard least-squares fit to a white noise residual and a new, and clearly superior, fit assuming a brown noise residual. Both time and frequency domain approaches give comparable results and contribute to a significant lowering of the residual level in non-tidal bands.     

Dynamics of the transport of the phosphorus and silicon at the water-bottom boundary in the Baltic Sea

The study of the fine structure of the phosphorus and silicon distribution in near-bottom layers and in the interstitial water of the sediments has been carried out in the different Baltic Sea regions (Gulf of Finland, Bornholm, Gotland). The data of this study are used to calculate the flows and effective transport coefficients for mineral phosphorus and silicon exchange processes between sediment and near-bottom layer. The values of nutrient flows varied depending on sediment type from 9.8 to 632 μg-at. m⁻² year⁻¹ for phosphorus and from 232.4 to 1881.1 μg-at. m⁻² year⁻¹ for silicon. The dependence of the effective transport coefficients versus the distance from the bottom (h) is expressed by empirically-derived equation: K_eff = Ah^−b. The values of constants “A” and “b” depend on the hydrochemical conditions, sediment type and hydrophysical conditions in the near-bottom layers. Calculated constants for regions are discussed.     

Very high-frequency and seasonal cave atmosphere PCO2 variability: Implications for stalagmite growth and oxygen isotope-based paleoclimate records

Cave air P_CO2 at two Irish sites varied dramatically on daily to seasonal timescales, potentially affecting the timing of calcite deposition and consequently climate proxy records derived from stalagmites collected at the same sites. Temperature-dependent biochemical processes in the soil control CO₂ production, resulting in high summer P_CO2 values and low winter values at both sites. Large Large-amplitude, high-frequency variations superimposed on this seasonal cycle reflect cave air circulation. Here we model stalagmite growth rates, which are controlled partly by CO₂ degassing rates from drip water, by considering both the seasonal and high-frequency cave air P_CO2 variations. Modeled hourly growth rates for stalagmite CC-Bil from Crag Cave in SW Ireland reach maxima in late December (0.063 μm h^− 1) and minima in late June/early July (0.033 μm h^− 1). For well-mixed ‘diffuse flow’ cave drips such as those that feed CC-Bil, high summer cave air P_CO2 depresses summer calcite deposition, while low winter P_CO2 promotes degassing and enhances deposition rates. In stalagmites fed by well-mixed drips lacking seasonal variations in δ¹⁸O, integrated annual stalagmite calcite δ¹⁸O is unaffected; however, seasonality in cave air P_CO2 may influence non-conservative geochemical climate proxies (e.g., δ¹³C, Sr/Ca). Stalagmites fed by ‘seasonal’ drips whose hydrochemical properties vary in response to seasonality may have higher growth rates in summer because soil air P_CO2 may increase relative to cave air P_CO2 due to higher soil temperatures. This in turn may bias stalagmite calcite δ¹⁸O records towards isotopically heavier summer drip water δ¹⁸O values, resulting in elevated calcite δ¹⁸O values compared to the ‘equilibrium’ values predicted by calcite–water isotope fractionation equations. Interpretations of stalagmite-based paleoclimate proxies should therefore consider the consequences of cave air P_CO2 variability and the resulting intra-annual variability in calcite deposition rates.