Interactive effects of ontogeny, food ration and temperature on elemental incorporation in otoliths of a coral reef fish

The potential for environmental and physiological modification of elemental incorporation in otoliths is significant and must be validated before otoliths can be used reliably to estimate water parameters over the life history of a fish. We experimentally manipulated temperature and diet quantity for juvenile, sub-adult, and adult Acanthochromis polyacanthus, a tropical damselfish of the SW Pacific. Significant interactive effects between life history stage, temperature and food quantity were observed for otolith Ba/Ca, while significant interactions between stage and food were observed for Sr/Ca. Specific growth rates were negatively correlated with D_Ba and D_Sr for juveniles and sub-adults. These interactions indicated elemental incorporation dynamics varied depending on the life history stage, suggesting variation in effects of stage-specific metabolism or reproductive status. Our results highlight complex responses of elemental incorporation to both endogenous and exogenous factors. Interpretations of life history transects across otoliths must account for these effects to avoid confounding environmental variability with ontogenetic changes in physiology.     

Allometric constraints on Sr/Ca and Ba/Ca partitioning in terrestrial mammalian trophic chains

In biological systems, strontium (Sr) and barium (Ba) are two non-essential elements, in comparison to calcium (Ca) which is essential. The Sr/Ca and Ba/Ca ratios tend to decrease in biochemical pathways which include Ca as an essential element, and these processes are termed biopurification of Ca. The quantitative pathway of the biopurification of Ca in relation to Sr and Ba between two biological reservoirs (R _n and R_{n -1}) is measured with an observed ratio (OR) expressed by the (Sr/Ca) _Rn /(Sr/Ca) _Rn-1 and (Ba/Ca) _Rn /(Ba/Ca) _Rn-1 ratios. For a mammalian organism, during the whole biopurification of Ca starting with the diet to the ultimate reservoir of Ca which is the bone, the mean values for OR_Sr and OR_Ba are 0.25 and 0.2, respectively. In this study, published Sr/Ca and Ba/Ca ratios are used for three sets of soils, plants, and bones of herbivorous and carnivorous mammals, each comprising a trophic chain, to illustrate the biopurification of Ca at the level of trophic chains. Calculated OR_Sr and OR_Ba of herbivore bones in relation to plants and of bones of carnivores in relation to bones of herbivores give OR_Sr=0.30±0.08 and OR_Ba=0.16±0.08, thus suggesting that trophic chains reflect the Sr/Ca and Ba/Ca fluxes that are prevalent at the level of a mammalian organism. The slopes of the three regression equations of log(Sr/Ca) vs. log(Ba/Ca) are similar, indicating that the process of biopurification of Ca with respect to Sr and Ba is due to biological processes and is independent of the geological settings. Modifications of the logarithmic expression of the Sr/Ca and Ba/Ca relationship allow a new formula of the biopurification process to be deduced, leading to the general equation OR_Ba=OR_Sr^1.79±0.33,where the allometric coefficient is the mean of the slopes of the three regression equations. Some recent examples are used to illustrate this new analysis of predator-prey relations between mammals. This opens up new possibilities for the utilization of Ba/Ca and Sr/Ca in addition to stable isotope ratios (¹³C and ¹⁵N) for the determination of the relative contribution of different food sources to an animals diet.     

Fish otolith chemistry influenced by exposure to multiple environmental variables

There is an increasing desire for researchers to use the elemental concentrations in fish otoliths to reconstruct environmental histories of fish. These reconstructions may be plausible due to the unique incorporation of elements into discrete layers of otolith material that correspond to daily growth, and because environmental variables of temperature, salinity, and water chemistry can influence otolith chemistry. However, it is essential to establish exactly how temperature, salinity, and the ambient concentration of elements influence otolith chemistry in order to interpret environmental histories of fish. Using a controlled laboratory experiment we tested the relative and interactive effects of temperature, salinity, and ambient concentration of strontium (Sr) and barium (Ba) on the resulting concentration of Sr and Ba in otoliths of black bream Acanthopagrus butcheri (Munro 1949). Salinity and concentration, and temperature and concentration interacted to affect the elemental concentration of Sr:Ca and Ba:Ca in otoliths. Regression analysis revealed that temperature and ambient concentration contributed most to the trend in otolith chemistry for both elements. Importantly, this is the first experiment to combine three environmental variables and assess their effect on otolith chemistry. Based on these results, it should be possible to use changes in the elemental concentration in otoliths to better reconstruct previous environments of temperature, salinity, and ambient water chemistry, which is especially useful when determining occupancy in habitats such as estuaries that display variable environmental characteristics.     

The Study of Impedance and Conductivity of New Modified Polystyrene Used as an Effective Adsorbent of Ba(II) Ions

In the research described here we prepared a novel, modified polystyrene (PS) with iminoether as the complexing agent for Ba²⁺. Most heavy metals cause environmental, atmospheric pollution.^[1–2] They cause consequence for humans health and aquatic life due to their toxicity. They become strongly toxic by mixing with different environmental elements and their removal from contaminated water is very important. The structure of all modified polystyrene such as nitrated polystyrene (PS−NO₂), aminated polystyrene (PS−NH₂), aminated polystyrene with imidate group (PS−NH−Im) and the complex with barium metal (PS−NH−Im/Ba²⁺) were analyzed by Fourier transform infrared spectroscopy (FT-IR), and the formation of N-2-Benzimidazolyl iminoether grafted PS was proved. The thermal stability and structure of the polystyrene and modified polystyrene were studied by differential thermal analysis (DTA) and X-ray diffractometry (XRD), respectively. The elemental analysis was used for the determination of the chemical composition of the modified PS. The grafted polystyrene was used in order to adsorb barium from wastewater with an acceptable cost before the wastewater distribution in the environment. The impedance analysis of the polystyrene complex PS−NH−Im/Ba²⁺ indicated an activated thermal conduction mechanism.The conductivity analysis of the complex with barium metal PS−NH−Im/Ba²⁺ was studied; the activation energy was deduced from an Arrhenius plot and corresponded to, , suggesting PS−NH−Im/Ba²⁺ was a proton-type of semiconductor.     

The biological production of marine suspended barite and the barium cycle in the Western Mediterranean Sea

Suspended particulate barium was measured in the Western Mediterranean along 4 profiles sampled during the PHYCEMED 1 cruise in 1981. The non-terrigenous fraction of particulate barium (i.e. excess Ba; Ba_xs) can account for up to 96% of total barium. This fraction follows the barite settling and dissolution rate model we described earlier for the Atlantic Ocean, confirming barite as the carrier of excess barium. We propose that these Ba_xs concentrations, which are higher in the Western Mediterranean than in the overall Atlantic, may represent an adaptation of the microplankton to the high densities and density gradients of surface Mediterranean waters.A mass-balance for Ba in the Mediterranean Sea shows: (1) that the atmospheric source must be much more important than previously reported: (2) that contrary to the Atlantic situation, the internal recycling of barium is of little importance compared to the flow of barium through the system.     

Otolith chemistry of prey fish consumed by a fish predator: does digestion hinder Russian doll techniques?

The effect of digestion by a predatory fish (largemouth bass Micropterus salmoides) on stable isotopic (δ¹³C and δ¹⁸O) and trace elemental (Sr:Ca and Ba:Ca) compositions of prey fish (bluegill Lepomis macrochirus) otoliths was investigated in a laboratory experiment. Trace element and stable‐isotopic signatures of L. macrochirus otoliths were not significantly altered for up to 16 h after L. macrochirus were consumed by M. salmoides. Prey fish otoliths recovered from predator digesta can retain environmental stable isotopic and trace elemental signatures, suggesting that determination of environmental history for prey fishes by stable‐isotope and trace‐element analysis of otoliths recovered from stomachs of piscivorous fishes will be feasible.     

Differences in the Trace Element Deposition in Otoliths Between Marine- and Freshwater-resident Japanese Eels, Anguilla japonica, as Determined by Laser Ablation ICPMS

Synopsis In order to determine whether the trace element composition in otolith of the Japanese eel Anguilla japonica could be used to determine its habitat use, we used laser ablation inductivity coupled plasma mass spectrometry (LA-ICPMS) to assay sectioned otoliths of both marine-resident (sea eels) and freshwater-resident (river eels) eels. A close linear relationship in the Sr:Ca ratios between EPMA (X-ray analysis with an electron microprobe) and LA-ICPMS analyses was found, suggesting that the latter technique could be used to separate the marine and freshwater life phases. Elemental signatures in the otolith outside the elver mark showed significant differences in Cr:Ca, Mn:Ca, and Ba:Ca ratios as well as Sr:Ca ratios between sea and river eels. These results indicate that the elemental compositions may reflect environmental variability between marine and fresh water masses. Thus, those elemental ratios determined by LA-ICPMS analysis seem to have the potential to help distinguish the habitat of the eel.     

Synthesis and structure of two polymeric barium-oxydiacetates: [Ba(oda) · H2O]n and [Ba(Hoda)2]n (H2oda: oxydiacetic acid)

The reaction of barium carbonate or hydroxide with oxydiacetic acid leads to the self-assembly of two barium oxydiacetate polymers in good yield: [Ba(oda) · H₂O]_n (1) and [Ba(Hoda)₂]_n (2). The products have been characterized by elemental analysis, IR, TGA and single crystal X-ray diffraction studies. The central barium atom in each mononuclear fragment is nine-coordinate in 1 and 10-coordinate in 2. These fragments are bridged by carboxylato groups in anti-anti conformation and through H-bonds bonding interactions forming complex 3D networks.     

Potential Effects of Hydroelectric Dam Development in the Mekong River Basin on the Migration of Siamese Mud Carp (Henicorhynchus siamensis and H. lobatus) Elucidated by Otolith Microchemistry

The migration of Siamese mud carp (Henicorhynchus siamensis and H. lobatus), two of the most economically important fish species in the Mekong River, was studied using an otolith microchemistry technique. Fish and river water samples were collected in seven regions throughout the whole basin in Thailand, Laos and Cambodia over a 4 year study period. There was coherence between the elements in the ambient water and on the surface of the otoliths, with strontium (Sr) and barium (Ba) showing the strongest correlation. The partition coefficients were 0.409–0.496 for Sr and 0.055 for Ba. Otolith Sr-Ba profiles indicated extensive synchronized migrations with similar natal origins among individuals within the same region. H. siamensis movement has been severely suppressed in a tributary system where a series of irrigation dams has blocked their migration. H. lobatus collected both below and above the Khone Falls in the mainstream Mekong exhibited statistically different otolith surface elemental signatures but similar core elemental signatures. This result suggests a population originating from a single natal origin but bypassing the waterfalls through a passable side channel where a major hydroelectric dam is planned. The potential effects of damming in the Mekong River are discussed.     

Spatial and temporal variations in otolith chemistry and relationships with water chemistry: a useful tool to distinguish Atlantic salmon Salmo salar parr from different natal streams

Otolith elemental (Sr:Ca, Ba:Ca, Mn:Ca, Mg:Ca and Rb:Ca) and isotopic (⁸⁷Sr:⁸⁶Sr) profiles from several annual cohorts of juvenile Atlantic salmon Salmo salar were related to the physico‐chemical characteristics (chemical signatures, flow rate, temperature and conductivity) of their natal rivers over an annual hydrological cycle. Only Sr:Ca, Ba:Ca and ⁸⁷Sr:⁸⁶Sr in otoliths were determined by their respective ratios in the ambient water. Sr:Ca ratios in stream waters fluctuated strongly on a seasonal basis, but these fluctuations, mainly driven by water flow regimes, were not recorded in the otoliths. Otolith Sr:Ca ratios remained constant during freshwater residency at a given site and were exclusively related to water Sr:Ca ratios during low flow periods. While interannual differences in otolith elemental composition among rivers were observed, this variability was minor compared to geographic variability and did not limit classification of juveniles to their natal stream. Success in discriminating fish from different sites was greatest using Sr isotopes as it remained relatively constant across years at a given location.     

Growth rate and age effects on Mya arenaria shell chemistry: Implications for biogeochemical studies

The chemical composition of bivalve shells can reflect that of their environment, making them useful indicators of climate, pollution, and ecosystem changes. However, biological factors can also influence chemical properties of biogenic carbonate. Understanding how these factors affect chemical incorporation is essential for studies that use elemental chemistry of carbonates as indicators of environmental parameters. This study examined the effects of bivalve shell growth rate and age on the incorporation of elements into juvenile softshell clams, Mya arenaria. Although previous studies have explored the effects of these two biological factors, reports have differed depending on species and environmental conditions. In addition, none of the previous studies have examined growth rate and age in the same species and within the same study. We reared clams in controlled laboratory conditions and used solution-based inductively coupled plasma mass spectrometry (ICP-MS) analysis to explore whether growth rate affects elemental incorporation into shell. Growth rate was negatively correlated with Mg, Mn, and Ba shell concentration, possibly due to increased discrimination ability with size. The relationship between growth rate and Pb and Sr was unresolved. To determine age effects on incorporation, we used laser ablation ICP-MS to measure changes in chemical composition across shells of individual clams. Age affected incorporation of Mn, Sr, and Ba within the juvenile shell, primarily due to significantly different elemental composition of early shell material compared to shell accreted later in life. Variability in shell composition increased closer to the umbo (hinge), which may be the result of methodology or may indicate an increased ability with age to discriminate against ions that are not calcium or carbonate. The effects of age and growth rate on elemental incorporation have the potential to bias data interpretation and should be considered in any biogeochemical study that uses bivalves as environmental indicators.     

Potassium and other minor elements in Porites corals: implications for skeletal geochemistry and paleoenvironmental reconstruction

We investigated how the K/Ca, Na/Ca, Mg/Ca, and Sr/Ca ratios of powders ground from Porites coral skeletons are changed by cumulative chemical treatments to the powders: first with distilled/deionized water (DDW), next with 30?% H₂O₂ and then with 0.004?mol?l^?1 HNO₃. The K/Ca, Na/Ca, and Mg/Ca ratios were decreased with the DDW treatment and then increased with the H₂O₂ and HNO₃ treatments; the Sr/Ca ratio was slightly decreased through the cumulative treatments, suggesting fine-scale (tens of ??m or less) elemental heterogeneities in the skeleton??K, Na, and Mg are significantly enriched at the skeletal surface and also at the center of calcification (COC); in contrast, the heterogeneity of Sr is very small. We suggest that the principal mechanisms of K incorporation into coral skeleton are (1) ion incorporation into lattice defects/distortions and (2) ion adsorption onto crystal discontinuities (including crystal?Corganic matter interfaces) as forms of K⁺ and KSO₄ ^?. Furthermore, we measured the element/Ca ratios of a modern Porites coral skeleton along its growth direction at 2-mm intervals. Results showed that all the element/Ca ratios displayed annual cycles, that the K/Ca and Na/Ca ratios covaried with each other, and that the annual-minimum K/Ca and Na/Ca ratios coincided with the annual high-density band in the skeleton. It is unclear what environmental factors may cause the covarying annual cycles of the K/Ca and Na/Ca ratios; however, as a possible explanation, the cycles may be due not to environmental factors, but to a combined effect of (1) the K and Na enrichment at the COC, (2) annual bands of high- and low-density skeleton, and (3) mm-scale element/Ca measurements along the skeletal growth direction. This kind of effect on geochemical proxies of which the concentrations significantly differ between the COC and surrounding skeleton may generate false or distorted paleoenvironmental signals.     

Small-scale spatial variation in the elemental composition of otoliths of Stegastes nigricans (Pomacentridae) in French Polynesia

Solution-based inductively coupled plasma-mass spectrometry (ICP-MS) was used to determine if Stegastes nigricans collected from 15 sites in French Polynesia could be distinguished by the trace element composition of their otoliths. A total of 293 adults were collected by spearing and their otoliths were analysed. We found that elemental signatures differed significantly among sites within and between the islands of Tahiti and Moorea (p<0.001), primarily due to variation in concentrations of the elements Ba, Ca, Li, Mg, Mn, Na, Sr and Y. The otoliths of fish collected within Papeete Harbour in Tahiti had distinctive elemental signatures characterised by relatively high concentrations of Mn. Otoliths of these fish could be distinguished from others that were collected only a small distance (200 m) from the harbour. This is the first time that differences in chemical composition of otoliths have been reported at such small spatial scales and this trait may prove useful for the studies of connectivity of populations at within reef scales.     

Analysis of otolith chemistry in Nassau grouper (Epinephelus striatus) from the Bahamas and Belize using solution-based ICP-MS

 We examined the utility of otolith minor and trace element chemistry, assayed with inductively coupled plasma mass spectrometry (ICP-MS), as a means of delineating population structure in the Nassau grouper (Epinephelus striatus). We characterized the elemental composition of otoliths collected in 1993 from three locations in Exuma Sound, Bahamas and from Glover Reef, Belize in 1995. A single location in Exuma Sound was sampled in 1994 to test temporal variability in otolith composition. Five elements (Ca, Zn, Sr, Ba and Pb) were routinely detected, at levels significantly above background, by solution-based ICP-MS. Results from analysis of variance of elemental data, expressed as a ratio to Ca, indicated that there were no significant differences among the Exuma locations for any element, but significant variability was found between Glover Reef and the pooled Exuma localities for Zn/Ca, Sr/Ca and Ba/Ca ratios. Significant inter-annual differences at one Exuma Sound location was restricted to Ba/Ca ratios. Discriminant function analysis correctly classified 86% and 95% of the Belize and pooled Exuma sites, respectively. Otoliths from Belize were characterized by low Zn/Ca and high Ba/Ca and Pb/Ca ratios compared to otoliths from fish collected in Exuma Sound. Although differences in Ba levels may be related to upwelling at Glover Reef, more data are needed to definitely link otolith composition with regional differences in water chemistry. Accepted: 15 February 1999     

Elemental signatures of Acanthochromis polyacanthus otoliths from the Great Barrier Reef have significant temporal, spatial, and between-brood variation

We evaluated the spatial and temporal scales over which otolith signatures varied in a reef fish on the Great Barrier Reef (GBR) using the non-dispersing damselfish Acanthochromis polyacanthus. We found a robust multi-element separation in otolith signatures from reef clusters in the northern and southern GBR. Variance components indicated that this spatial scale accounted for the majority of the variation in two elemental ratios (Ba/Ca and Sr/Ca) over the 2 years of the study. There was also significant variation in elemental signatures between otoliths collected over two consecutive years, as well as within a season. Individual reefs within clusters were less distinguishable based on otolith chemistry and were probably observed by differences within reefs (among sites and broods within sites). These results indicate that it may be difficult to determine the reef of origin for individual fish using otolith chemistry, while determining natal region seems a realistic goal.     

Expression of calcium channels in Xenopus oocyte injected with crab skeletal muscle fibre mRNA

Summary— Using the whole cell voltage-clamp technique and a Cl free and Na free Ba methane sulfonate solution, stage V and VI Xenopus oocytes demonstrated a Ba current (endogenous component) with a peak amplitude average of 6 nA (6 ± 2 nA). When oocytes were injected with crustacean skeletal muscle mRNA, an additional component of I_Ba could be detected (exogenous I_Ba). The latter current could be distinguished from the native one by several electrophysiological means: a peak amplitude average of 90 nA (90 ± 4 nA), activation potential threshold, steady state inactivation properties and sensitivity to Ca blockers. As shown by Jdaïâa and Guilbault in crustacean skeletal muscle fibres, exogenous I_Ba could be divided into two components: a “fast component” and a “slow component” probably passing through two types of Ca channels (fast and slow) since the peak Ba current voltage relationship was biphasic and the fast component of exogenous I_Ba was less sensitive than the slow to nifedipine. The features of the newly synthesized channels incorporated in the Xenopus oocyte membrane suggest that they may be associated with fast and slow channels, previously described in many preparations, particularly in crustacean skeletal muscle fibres.     

Effect of salinity on the skeletal chemistry of cultured scleractinian zooxanthellate corals: Cd/Ca ratio as a potential proxy for salinity reconstruction

The effect of salinity on the elemental and isotopic skeletal composition of modern zooxanthellate scleractinian corals (Acropora sp., Montipora verrucosa and Stylophora pistillata) was investigated in order to evaluate potential salinity proxies. Corals were cultured in the laboratory at three salinities (36, 38 and 40). The other environmental parameters were kept constant. For all species analyzed, Sr/Ca, Mg/Ca, U/Ca and Li/Ca ratios were not influenced by salinity changes. The Ba/Ca ratio also lacks a systematic relationship with salinity and exhibits high inter-generic variations, up to one order of magnitude. On the contrary, the Cd/Ca ratio decreases as a function of increasing salinity, and δ¹⁸O and δ¹³C also presented a significant response, but with opposite trends to salinity variations. Since Cd/Ca is usually considered as an upwelling proxy, its salinity dependence could compromise the upwelling signal, unless some corrections can be carried out. Regardless, if the dependence found in the present dataset proved to be widespread and systematic, the Cd/Ca ratio could represent a promising salinometer awaiting further investigation. This study also confirmed the reliability of the well-established temperature proxies Sr/Ca, Mg/Ca and U/Ca, as these ratios were insensitive to salinity variations. Moreover, our results showed that δ¹⁸O or δ¹³C can be considered as reliable temperature recorders as far as the salinity effect is removed from the parameter reconstructed (e.g., temperature). Investigating the influence of salinity on the skeletal chemistry of scleractinian corals grown under controlled environmental conditions confirmed previous results, validated isotopic corrections, and identified a promising proxy of salinity.     

Selectivity in biomineralization of barium and strontium

The desmid green alga Closterium moniliferum belongs to a small number of organisms that form barite (BaSO₄) or celestite (SrSO₄) biominerals. The ability to sequester Sr in the presence of an excess of Ca is of considerable interest for the remediation of ⁹⁰Sr from the environment and nuclear waste. While most cells dynamically regulate the concentration of the second messenger Ca²⁺ in the cytosol and various organelles, transport proteins rarely discriminate strongly between Ca, Sr, and Ba. Herein, we investigate how these ions are trafficked in C. moniliferum and how precipitation of (Ba,Sr)SO₄ crystals occurs in the terminal vacuoles. Towards this goal, we simultaneously visualize intracellular dynamics of multiple elements using X-ray fluorescence microscopy (XFM) of cryo-fixed/freeze-dried samples. We correlate the resulting elemental maps with ultrastructural information gleaned from freeze-fracture cryo-SEM of frozen-hydrated cells and use micro X-ray absorption near edge structure (micro-XANES) to determine sulfur speciation. We find that the kinetics of Sr uptake and efflux depend on external Ca concentrations, and Sr, Ba, and Ca show similar intracellular localization. A highly ion-selective cross-membrane transport step is not evident. Based on elevated levels of sulfate detected in the terminal vacuoles, we propose a “sulfate trap” model, where the presence of dissolved barium leads to preferential precipitation of (Ba,Sr)SO₄ due to its low solubility relative to SrSO₄ and CaSO₄. Engineering the sulfate concentration in the vacuole may thus be the most direct way to increase the Sr sequestered per cell, an important consideration in using desmids for phytoremediation of ⁹⁰Sr.     

Extrinsic factors affecting otolith chemistry – implications for interpreting migration patterns in a diadromous fish

Much has been revealed about fish migration, including diadromous behaviour, through the use of otolith chemistry. Manipulative experiments assist with unravelling information on otolith chemical composition and incorporation thereby answering specific questions on diadromous movements. In this study, a laboratory-based experiment was used to determine the relative and interactive effects of salinity and water temperature on the composition of three key elements (Sr, Ba and Mg) within the otolith of a catadromous fish, Percalates novemaculeata, endemic to south-eastern Australia. Otolith incorporation of Sr and Ba was positively related to ambient water concentration, whereas Mg incorporation was not. Sr and Ba increased and decreased significantly across salinity gradients, respectively, with minor positive effects of temperature also being detected. Salinity and temperature interacted to significantly affect the elemental concentration ratios for Ba: Ca in otoliths. Discrimination between fresh water and marine environments shows promise for interpreting P. novemaculeata residency based on these elements alone. However, deciphering finer scale movements within estuarine environments may be difficult. Our data highlights the importance of multifactorial validation experiments and suggests complementary use of multiple approaches for unravelling species-specific patterns of fish movement and habitat use.