Ecological Archives E094-127-D1

M. Lebrato, J. B. McClintock, M. O. Amsler, J. B. Ries, H. Egilsdottir, M. Lamare, C. D. Amsler, R. C. Challener, J. B. Schram, C. L. Mah, J. Cuce, B. J. Baker. 2013. From the Arctic to the Antarctic: the major, minor, and trace elemental composition of echinoderm skeletons. Ecology 94:1434. http://dx.doi.org/10.1890/12-1950.1


Introduction

Biological calcification is the process by which marine organisms produce their shells, skeletons, or tests from the low-Mg calcite (< 4% MgCO3), high-Mg calcite (> 4% MgCO3), and/or aragonite polymorphs of CaCO3. These calcified structures protect marine calcifiers from predation, provide ballast for maintaining the organism’s position in the water column or seafloor, may serve as waste repository for excess Ca2+, and may function to buffer the organisms’ internal fluids during times of oxidative stress. Biological calcification is also an important component of the Earth's carbon cycle (Ridgwell 2005), providing a mechanism for transporting dissolved inorganic carbon from the water column to the seafloor and storing it there as limestone.

Atmospheric carbon dioxide (pCO2) has increased from approximately 280 to nearly 400 ppm since the Industrial Revolution in the late 1700s (Keeling, 1960; Neftel et al. 1985; Keeling et al. 2009), largely due to the anthropogenic combustion of fossil fuels and to deforestation. This rate of increase is at least 10 times greater than what is thought to have occurred over the past several million years (Doney and Schimel 2007), resulting in a current atmospheric pCO2 that represents the highest level in at least the past 800,000 years (Luthi et al. 2008). This largely anthropogenic increase in atmospheric pCO2 has caused the pH of surface seawater to decrease by approximately 0.1 units since the Industrial Revolution (Raven et al. 2005). If atmospheric pCO2 reaches the 800 ppm level that the Intergovernmental Panel on Climate Change (Houghton et al. 2001) predicts will occur by the end of the 21st century, then the pH of high-latitude surface seawater will decrease by another 0.3–0.4 units (Brewer 1997; Feely et al. 2004), resulting in a nearly 50% reduction in the carbonate ion concentration of seawater. An aqueous system’s affinity for calcification can be quantified by its CaCO3 saturation state (ΩCaCO3):

ΩCaCO3 = [Ca2+][CO32-]/K*sp,

where [Ca2+] and [CO32-] are concentrations of calcium and carbonate ions and K*sp is the stoichiometric solubility product of the appropriate polymorph of CaCO3 (aragonite or calcite). Thus, the predicted decline in [CO32-] will reduce seawater ΩCaCO3, potentially making it more difficult for many calcifying marine organisms to produce and maintain their shells and skeletons.

Carbonate production in many benthic marine ecosystems is dominated by Echinodermata (Lebrato et al. 2010), a phylum that radiated in the early Palaeozoic (520 Ma), with the oldest fossils dating back to the early Cambrian (Ubaghs 1975). Echinoderm diversity increased during the middle Cambrian (Sprinkle 1973) and the phylum largely survived the Permian-Triassic extinction (250 Ma). Echinoderm fossils are best-preserved in limestone units (Kroh and Nebelsick 2010). In Quaternary deposits, they are found in most marine sediments—ranging from the intertidal zone to the abyssal plain (Lebrato et al. 2010). Five classes comprise the modern Echinoderm phylum: Asteroidea, Echinoidea, Ophiuroidea, Holothuroidea, and Crinoidea. Representatives of these classes are found across large bathymetric gradients (Howell et al. 2002), from the intertidal zone to the abyssal plain.. Echinoderms are typically considered keystone members of marine ecosystems because of their ability to limit algal growth on benthic marine surfaces. They also play key role in carbonate mineralization and export in the oceans (Lebrato et al. 2010).

Echinoderms produce calcite with high proportions of Mg2+ ions (high-Mg calcite), ranging from 4 to 30 mol-% MgCO3 (Vinogradov 1953; Weber 1973). Because of the relatively high Mg-content and, thus, high solubility (Morse et al. 2006) of echinoderms’ calcareous components, CO2-induced ocean acidification may cause impair their process of calcification (e.g., Ries et al. 2009; Courtney et al. 2013) and even result in dissolution of their tests. In addition to Mg, numerous other elements (major, trace, and minor) are incorporated into echinoderm calcite that should influence its solubility in seawater (e.g., Li, Be, Mg, Al, P, S, K, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Zr, Mo, Ag, Cd, Sn, Sb, Te, Ba, La, Ce, Nd, Dy, W, Re, Au, Hg, Tl, Pb, Bi, and U). Thus, systematic quantification of the concentration of these elements in echinoid calcite is needed to better model and predict the echinoderm response to CO2-induced ocean acidification.

Furthermore, as echinoderm calcification slows and/or echinoderm Mg-calcite begins to actively dissolve, these major, minor and trace elements that are typically incorporated into echinoderm calcite would become enriched in the seawater. To estimate how the flux and concentrations of these elements in the oceans will be impacted by CO2-induced ocean acidification, we must first quantify the concentrations of these elements in the shells and skeletons of the major carbonate-sediment-producing organisms, such as the echinoderms.

Systematic quantification of the elemental compositions of echinoderm tests that we collected across strong thermal and pH gradients throughout the oceans should also improve our understanding of the relationship between seawater parameters (e.g., pH and temperature) and elemental partitioning within echinoderm calcite, which should expand the applicability of echinoderm tests as geochemical monitors of paleoceanographic change.

To date, the use of echinoderms in paleoceanographic reconstructions has been limited to the interpretation of echinoderm calcite Mg/Ca as a proxy of paleoseawater Mg/Ca (Dickson 2004; Ries 2004). Although Borremans et al. (2009) recently demonstrated through culture experiments that echinoid Mg/Ca responds to seawater salinity, this potential paleoproxy has yet to be applied to fossil echinoderms.

Owing to the high quality of preservation of echinoderm calcite (Dickson 2004), echinoderms may prove to be reliable geochemical monitors for a broader range of seawater properties, including seawater pH from B/Ca (e.g., Yu et al. 2007), seawater temperature from Sr/Ca (e.g., Chave 1954), sedimentary influx from Al/Ca (e.g., Bastidas and Garcia 1999) and Ba/Ca (Prouty et al. 2008), among others.

A thorough characterization of echinoderms' elemental geochemistry should improve our understanding of how echinoderms will respond to CO2-induced ocean acidification, better constrain elemental flux in the oceans, and potentially expand the range of paleoceanographic reconstructions that can be made from elemental ratios within fossil echinoderms.

Controls on skeleton content

In order to interpret major, minor, and trace elemental ratios in echinoderm calcite, we consider two generalized views of how echinoderm skeletal chemistry is controlled: (1) environmental control and (2) genotypic control

(1) "Environmental control": Non-genetic factors that control elemental incorporation into echinoderm Mg-calcite, including seawater temperature, salinity, composition, carbonate chemistry, and/or rate of calcification. Mg and Sr, for instance, are two of the most commonly studied co-precipitates of biogenic calcite because of their relatively high concentrations in that mineral and because of their utility as seawater paleothermometers in biogenic and abiogenic carbonates. Myriad studies have investigated the effects of temperature and ΩCaCO3 on Mg- and Sr-partitioning in CaCO3, but for the sake of brevity, only a handful are discussed here.

Precipitation experiments have revealed that Mg/Ca varies proportionally with temperature (e.g., Chilingar 1962; Katz 1973; Füchtbauer and Hardie 1976; Burton and Walter 1987; Mucci 1987; Oomori et al. 1987) and that Sr/Ca varies inversely with temperature (e.g., Kinsman 1969; Kinsman and Holland 1969; Dickson 1985) in non-biological calcite. Laboratory experiments and field studies on calcifying marine organisms have also revealed that Mg/Ca varies proportionally with temperature (e.g., Chave 1954; Nürnberg et al. 1996; Lea et al. 1999; Kroh and Nebelsick 2010) and that Sr/Ca varies inversely with temperature (e.g., Lea et al. 1999) for calcite-secreting organisms.

Other experiments have shown that ΩCaCO3 has no effect on the Mg-content of either abiogenic (e.g., Mucci and Morse, 1983; Mucci et al. 1985; Hartley and Mucci, 1996; DeChoudens-Sanchez and Gonzalez 2009) or biogenic calcite (e.g., Dissard et al. 2010), although Lea et al. (1999) observed a direct correlation within calcitic foraminifera. Experiments have also shown that Sr/Ca varies proportionally with ΩCaCO3 for both abiogenic [e.g., (Lorens, 1981, 1978)] and biogenic calcite (e.g., Lea et al. 1999; Dissard et al. 2010).

Salinity has also been shown to influence Mg/Ca ratios within echinoderm calcite (Borremans et al. 2009). Seawater pH has been shown to influence B/Ca ratios in biogenic calcite (e.g., Yu et al. 2007). And fluvial sedimentary flux has been shown to influence Al/Ca (e.g., Bastidas and Garcia 1999) and Ba/Ca ratios (e.g., Prouty et al. 2008) within marine carbonates. Water masses have also been linked to Nd/Ca ratios within marine carbonates (e.g., Carter et al. 2010).

Long-term changes in seawater composition are an important environmental factor controlling the elemental composition of ancient marine carbonates. For example, seawater Mg/Ca (Mg/Caseawater) has oscillated between ca. 1.0 (e.g., Cretaceous time) to ca. 5.2 (modern ocean) throughout much of geologic time (Hardie 1996; reviewed by Ries 2010). Mg/Ca ratios in the ossicles of fossilized echinoderms have been shown to track these changes in Mg/Caseawater throughout most of Phanerozoic time (last 545 My; Dickson 2004).

The rate of calcification is also known to influence elemental incorporation into marine carbonates. For instance, seasonal food-driven variations in the calcification rates of mollusks, which are uncorrelated to seawater temperature and salinity, have been linked to cyclical fluctuations in shell elemental chemistry (Lorrain et al. 2005). Similarly, Sr/Ca ratios in scleractinian corals have been linked to rates of skeletal accretion (Cohen et al. 2002). The correlation between calcification rates and elemental incorporation within biogenic carbonates has traditionally been attributed to the organism’s reduced ability to discriminate against cations bearing a similar charge and size to the Ca2+ ion during periods of rapid calcification. The Ca2+-ATPase enzyme, for instance, has been implicated as the primary mechanism of exporting protons and importing Ca2+ ions into the coral calcifying fluid (Cohen and McConnaughey 2003). If higher calcification rates are accompanied by up-regulation of this enzyme, then the enzyme’s selectivity for Ca2+ ions may become compromised during these rapid-calcification intervals, leading to the accidental import of a greater proportion of non-Ca2+ ions into the calcifying fluid, which are ultimately incorporated with greater frequency into the calcareous skeleton.

However, more recent work has shown that not all major, minor, and trace elements increase within biogenic calcite as calcification rates increase; some actually decrease (Gaetani et al. 2011). Gaetani and Cohen (2006) invoked Rayleigh fractionation within the calcifying fluid of scleractinian corals to explain the inverse relationship between Mg/Ca and Sr/Ca observed within coral skeletons accreted over a range of calcification rates. They argued that since seawater Mg/Ca (5:1) is greater than coral aragonite Mg/Ca (<1:100), increased rates of calcification under elevated temperatures would effectively enrich the steady-state Mg/Ca ratio of the coral’s calcifying fluid, which would in turn cause higher Mg/Ca ratios to be recorded in the coral’s skeleton during more rapid calcification, thereby generating the direct correlation observed between seawater temperature and coral aragonite Mg/Ca. Conversely, since seawater Sr/Ca (0.9:100) is a bit less than coral aragonite Sr/Ca (≥ 1:100), calcification would effectively deplete the steady-state Sr/Ca ratio of the coral’s calcifying fluid, which would in turn cause lower Sr/Ca ratios to be recorded in the coral’s skeleton during more rapid calcification, thereby generating the inverse correlation observed between seawater temperature and coral aragonite Sr/Ca. However, the story would be slightly different for echinoderm calcite. Since Sr/Ca (0.1:100) and Mg/Ca (< 30:100) of echinoderm calcite (rather than coral aragonite) are both less than Sr/Ca (0.9:100) and Mg/Ca (5:1) of seawater, increased calcification within the calcifying fluid should enrich both Sr/Ca and Mg/Ca within the calcifying fluids and skeletons of echinoderms. This results in the direct correlation of both Sr/Ca and Mg/Ca with echinoderm calcification rate.

(2) "Genotypic control": A biological trait controlling elemental incorporation into echinoderm Mg-calcite, specific to individual echinoderm species and/or life-history stage and thus suggestive of a genetic trait that evolved in response to some environmental factor. For instance, different species of echinoderms have different Mg/Ca ratios within analagous skeletal elements (Chave 1954 and data presented herein). And even within an individual echinoderm, Mg/Ca ratios can vary widely amongst different skeletal elements, such as between the spines and test plates (Ries 2004). Elemental ratios in echinoderm Mg-calcite can also vary throughout the life-history of an individual organism (see data herein).

The elemental composition of echinoderms ultimately results from the synthesis of the environmental and genetic controls discussed above. However, there exists great uncertainty as to the interactions of these controls. For example, echinoderms are thought to produce amorphous calcium carbonate (ACC) as a precursor to their final Mg-calcite. Yet it is unclear whether the ultimate crystalline polymorph (Mg-calcite) and elemental composition of the echinoderm’s skeleton are defined upon production of the ACC or upon conversion of the ACC to Mg-calcite, and to what extent environmental and genetic factors control these dynamics.

Data set scope

We present major, minor, and trace elemental data for echinoderm specimens spanning the 5 classes of the echinoderm phylum: Asteroidea, Echinoidea, Ophiuroidea, Holothuroidea, and Crinoidea. Here we present high-resolution measurements of the elemental compositions of echinoderm Specimens were collected the Arctic to the Antarctic Oceans, and from surface waters to depths of 1200 m. The last major assessment of the elemental composition of echinoderms was undertaken by Vinogradov (1953). Our new data set was obtained using state-of-the-art analytical techniques that afford higher mass resolution, higher precision and accuracy, and lower detection limits. Thus, we were able to more accurately analyze a greater number of elements that spanned a broader mass range. These analyses should advance our understanding of echinoderms' role in elemental cycling in the oceans, their predicted response to ocean acidification, and their ability to geochemically monitor changes in the physical parameters of seawater, such as temperature, pH, and salinity. These analyses may also have implications beyond the field of marine sciences, such as in the materials sciences (e.g., echinoderm biomineralization as a model of ACC-based biomineralization and/or cementation) and in the fertilizer industry (e.g., echinoderm calcite as a source of lime-based fertilizer).

Metadata

Class I. Data set descriptors

A. Data set identity: Major, minor, and trace elemental composition of echinoderm skeletons

B. Data set identification code:

Full_trace_elemental_concentrations_ratios_Echinodermata

Full_trace_elemental_concentrations_ratios_latitude_Echinodermata

C. Data set description

Principal Investigators: Mario Lebrato, Helmholtz Centre for Ocean Research Kiel (GEOMAR). Germany.

James B. McClintock, University of Alabama at Birmingham. USA.

Justin B. Ries, University of North Carolina at Chapel Hill. USA.

Abstract: Biogenic carbonate production in benthic marine ecosystems is dominated by representatives of the Echinodermata. Carbon and other major, minor, and trace elements are exported to the seabed where they accumulate or dissolve. Preserved carbonates (Mg-calcite) have applications in oceanography and geochemistry and are used to reconstruct various parameters of ancient seawater, such as temperature (from Mg/Ca, Sr/Ca), seawater Mg/Ca (from Mg/Ca), and pH (from B/Ca). In general, the benthos is widely ignored for its role in the global carbon cycle despite the importance of echinoderms as a carbon sink (~ 0.1–0.2 Pg C/yr). Echinoderms produce their skeletons from Mg-calcite, which is more soluble than pure calcite and, therefore, more vulnerable to ocean acidification (OA). Little is known about the concentration of minor and trace elements within their tests, which can also destabilize the calcite lattice increasing the mineral’s solubility. Expanding our knowledge on their composition will improve our understanding of elemental flux in the oceans. Furthermore, establishing relationships between the physical parameters of seawater and minor/trace elemental ratios within echinoderm Mg-calcite should expand the utility of fossils, renowned for their high-quality preservation as geochemical archives. Herein, we present elemental composition data for Asteroidea (n = 108; 9 families, 23 species), Echinoidea (n = 94; 8 families, 12 species), Ophiuroidea (n = 24; 4 families, 5 species), Holothuroidea (n = 7; 3 families, 3 species), and Crinoidea (n = 3; 1 family, 1 species), collected from the Arctic to the Antarctic Oceans, from depths ranging from surface waters to 1200 m. The following elements were measured and normalized to [Ca]: Li, Be, Mg, Al, P, S, K, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Zr, Mo, Ag, Cd, Sn, Sb, Te, Ba, La, Ce, Nd, Dy, W, Re, Au, Hg, Tl, Pb, Bi, and U. Data are presented for the whole body, arms (plates), calcareous ossicles, spines, and test plates. Elements were quantified using inductively coupled plasma mass spectrometry. Our study presents the most comprehensive data set to date for a phylum whose skeletons are composed of Mg-calcite.

D. Key words: biomineralization; calcification; carbonate; Echinodermata; elemental composition; ICPMS; Mg-calcite; minor elements; ocean acidification; paleoceanography; paleoproxies; trace elements.

Class II. Research origin descriptors

A. Overall project description

Identity:

European Project on Ocean Acidification (EPOCA)

U.S. National Science Foundation, Office of Polar Programs, Grant title - The effects of ocean acidification and rising sea surface temperatures on shallow-water calcified benthic organisms in Antarctica.

U.S. National Science Foundation, Office of Biological Oceanography, Grant title - Investigation of the effects of CaCO3 saturation state & temperature on the calcification rate & skeletal properties of benthic calcifiers (#1031995)

Originators:

Mario Lebrato, Helmholtz Centre for Ocean Research Kiel (GEOMAR). Germany.

James McClintock, University of Alabama at Birmingham. USA.

Justin B. Ries, University of North Carolina at Chapel Hill. USA.

Period of Study:

2008–2013

Objectives:

The EU FP7 Integrated Project EPOCA (European Project on OCean Acidification) was launched in June 2008 for 4 years. The overall goal is to advance our understanding of the biological, ecological, biogeochemical, and societal implications of ocean acidification.

The U.S. NSF Office of Polar Programs effort was launched in June 2011 for 3 years. The overall goal is to advance our understanding of the prospective impacts of ocean acidification on Antarctic calcifying marine algae and invertebrates.

The U.S. NSF Biological Oceanography effort was launched in September 2010 for 3 years. The overall goal is to advance our understanding of the impacts of future ocean acidification on the calcification rates and skeletal properties of benthic marine calcifiers.

Summary:

EPOCA aims to:

- Document changes in ocean chemistry and biogeography across space and time.

- Determine the sensitivity of marine organisms, communities and ecosystems to ocean acidification.

- Integrate results on the impact of ocean acidification on marine ecosystems in biogeochemical, sedimentological, and coupled ocean-climate models to better understand and predict the responses of the Earth system to ocean acidification.

- Assess uncertainties, risks and thresholds ("tipping points") related to ocean acidification at spatial scales ranging from sub-cellular to ecosystem and from regional to global.

The U.S. NSF Office of Polar Programs effort has the following objectives:

- Compare the impacts of acidified and non-acidified seawater and seawater temperatures on growth, photosynthetic capacity, and bleaching in crustose corallines versus non-calcified crustose corallines.

- Compare the impacts of acidified and non-acidified seawater and seawater temperatures on growth, allocation of materials, and energy to body components, compensatory calcification, shell dissolution, behaviour and survival in gastropods.

The U.S. NSF Office of Biological Oceanography effort has the following objective:

- Investigate the impact that CO2-induced ocean acidification will have on the following properties of benthic marine calcifiers: (1) their rates of calcification and linear extension; (2) the relative abundance and micron-scale distribution of the various CaCO3 polymorphs within their shells/skeletons; (3) the ultrastructure and crystal morphology of their shells/skeletons; and (4) their biomechanical properties.

Sources of funding:

European Project on Ocean Acidification (EPOCA) to Mario Lebrato Ph.D work.

U.S. NSF Office of Polar Programs/ UAB Endowment to James McClintock.

U.S. NSF Office of Biological Oceanography to Justin Ries.

B. Specific subproject description

Study region and sampling: Echinoderms were collected using SCUBA, trawling, or remote operated vehicle from 2008 to 2011 from depths ranging from 2 to 1200 m from the Atlantic, Pacific, Arctic, and Southern Oceans (Table 1 and also see Lebrato et al. 2010 and McClintock et al. 2011). Individuals were measured and weighed, then dissected into various components including whole body, arms (plates; some Antarctic species), calcareous ossicles (in some holothurids), plates, or spines. Elemental analysis was conducted on cleaned and powdered skeletal elements (see Lebrato et al. 2010 and McClintock et al. 2011 for techniques). The majority of samples (> 70%) were collected from temperate and polar latitudes. All organisms were collected with required environmental permits. Samples were catalogued, placed into ziplock bags, and then frozen at either -20 or -80 °C before being shipped to home institutions for subsequent elemental analysis.

Experimental or sampling design: Samples were obtained during various cruises or were collected via SCUBA or snorkelling from subtidal or intertidal environments.

Research Methods:

Carbonate sample analysis: All samples except those from the sub-Arctic and Antarctic (Table 1) were stored and initially processed at the Helmholtz Centre for Ocean Research in Kiel (GEOMAR, Germany) and then shipped to the University of North Carolina, Chapel Hill (USA). Whole body samples were freeze-dried for 48 h and then pulverized into a fine powder (inorganic and organic material included). Some echinoids (depending on sample availability) were divided into plates and spines (only inorganic material included; see Table 1). Spines were removed using a razor blade and then pieces of the test were cut into smaller pieces with scissors. Samples were lightly ground in an agate mortar and pestle for 10-15 s. A 0.5 g sample of the pulverized echinoderm material was digested for 2 h in Aqua Regia at 90 °C in a microprocessor controlled digestion block. Elemental measurements were obtained using a Perkin Elmer Sciex ELAN 9000 inductively coupled plasma mass spectrometer (ICP-MS). Duplicate samples were run every 15 samples, in-house controls were run every 33 samples, and digested certified standards (for instrument calibration) and blanks were run every 68 samples. 

Samples collected in the sub-Arctic (Table 1) were analyzed at the Institute of Earth Sciences, University of Iceland. Samples were thawed and cleaned with distilled water and dried at room temperature for ~ 10 days. Ophiuroids and asteroids were dried as whole organisms, but organic matter (soft tissue) was removed from echinoids, leaving only calcified material (body parts, spines, and plates). Samples were powdered and sub-samples (approximately 1-10 mg) were dissolved in one ml of 65% ultra pure nitric acid.  Four ml of Milli-Q deionizedwater was then added to the solution. Organic material was removed by filtering with a Whatman 42 filter. Elemental analysis took place on a Spectro CIROS inductively coupled plasma optical emission spectroscope (ICP-OES). The analytical concentration range was linear over several orders of magnitude, starting in the ppb range for most elements. Standard solutions were made from NIST-traceable calibration solutions (Spex Industries Inc.). The standards used in 0.5 % nitric acid were 30 ppm (Ca and Mg), 2 ppm (Sr) and 10 ppm (Cl, Na, K, S, and P). The non-carbonate elements (Na, K, S, P and Cl), were monitored to estimate contamination levels. Low Cl and Na concentrations (below 1 ppm) indicated efficient cleaning. Samples were not weighed and thus only molar ratios are reported for the sub-Arctic species (Table 2)..

Samples collected in Antarctica (Table 1) were analyzed by Actlabs in Ancaster, Ontario (Canada) (www.actlabs.com). Sample treatment and methods are in McClintock et al. (2011). In brief, frozen samples were thawed and dissected. For asteroids and ophiuroids, arms (thus arm plates, which are comparable to other plate data in the present study) were cut and organic material was removed, except for two asteroids (Kampylaster incurvatus and Granaster nutrix) where whole body samples were analyzed (Table 1). These “whole body” results are not comparable to other specimens (Table 1) because the organic material was removed by soaking the tissues in sodium hypochlorite (NaClO; Fisher Scientific). For the holothurids, the calcareous ring was dissected. The echinoids were divided into spines and plates. All samples were soaked in 10% NaClO for a few days to remove organic matter. The remaining inorganic material was vacuumed onto filter paper rinsed with Milli-Q deionized water for several minutes. Filters were dried at 50 °C for 48 h and the material ground to a fine powder with an agate mortar and pestle. The powdered material was divided into 90-500 mg splits and dissolved in a mixture of nitric (HNO3) and hydrochloric acid (HCl) (HNO3:HCl molar ratio of 1:3) for 2 h at 95 °C. Samples were diluted with Milli-Q water. The analysis took place on a PerkinElmer inductively coupled plasma atomic emission spectroscope (ICP-AES) for Ca, Mg, and Sr. USGS standards were analyzed every 13 samples. Analytical accuracy was within 0.01 % of the standard value. Because initial samples were carefully weighed, results were reported as percentages of the dry weight in grams or moles, which were subsequently used to calculate molar ratios (relative to Ca).

Preparation of data sets: The data collated and stored in the ESA Ecological Archives (http://esapubs.org/archive) were measured in ppm or ppb (except subarctic samples that were originally measured as ratios). The only conversion was the normalization of these concentrations to Ca concentration (e.g., element/Ca), which was expressed either as mmol/mol or as µmol/mol.

In "Full_trace_elemental_concentrations_ratios_Echinodermata" a total of 8 terms have been collated. This is followed by elemental concentrations and ratios to Ca (46 elements and 45 ratios):

Class: The taxonomic class to which the echinoderm belongs.

Species: Species used.

Depth: Collection depth.

Latitude: Geographical latitude of collection.

Longitude: Geographical longitude of collection.

Collection method: Information on how the sample was obtained.

Location: Information on where the sample was obtained.

Skeleton part: Information about the body/skeleton part analyzed.

Element concentration (e.g. Ca): Concentration of the element in ppm or ppb.

Ratio (e.g. Li/Ca): Element/Ca ratio in mmol/mol or µmol/mol.

In " Full_trace_elemental_concentrations_ratios_latitude_Echinodermata" a total of 8 terms have been collated. The elemental concentrations and ratios are included in the last 3 terms:

Symbol: The corresponding symbol from the periodic table and the ratio to Ca (element/Ca).

Element: The element name written in full.

Atomic weight: The atomic weight of the element.

Units: The element concentration in ppm or ppb or the element/Ca ratio in mmol/mol or µmol/mol.

Detection limit: The analytical detection limit for the element and instrument.

Whole body: Element concentrations and ratios in whole body samples organized by taxonomic class and latitude. Data are as maximum (max.), minimum (min.), average (avg) and standard deviation (SD).

Spines: Element concentrations and ratios in whole body samples organized by taxonomic class and latitude. Data are as maximum (max.), minimum (min.), average (avg) and standard deviation (SD).

Plates + calcareous ring: Element concentrations and ratios in whole body samples organized by taxonomic class and latitude. Data are maximum (max.), minimum (min.), average (avg) and standard deviation (SD).

 

Class III. Data set status and accessibility

A. Status

Latest update:The data were measured in 2010 and 2011.

Latest Archive date:15 July 2012

Metadata status: The metadata are complete and up-to-date.

Data verification:All data have been checked and quality controlled.

B. Accessibility

Storage location and medium:Ecological Society of America data archives, http://esapubs.org/archive, the URL is published in each issue of its journals. The original data files exist on the primary author’s personal computer in MS Excel format. 

United States Data Acquisition Center archives all Antarctic data. The present database will be entered into this repository. 

Contact person:Mario Lebrato, Helmholtz Centre for Ocean Research Kiel (GEOMAR). Germany. Email: mlebrato13@gmail.com,  tel: +49 (0)431 600 4507.

Copyright restrictions:None.

Proprietary restrictions: None.

Costs: None.

Class IV. Data structural descriptors

TRACE ELEMENTAL CONCENTRATIONS & RATIOS

 

A. Data Set File

Identity: Full_trace_elemental_concentrations_ratios_Echinodermata

Size: 181 samples and measurements excluding header rows and separations rows.

Format and Storage mode: ASCII (comma-delimited), compressed and ZIP

Header information: The first 6 rows of the file name contain the variable names.

Alphanumeric attributes: Mixed

Special characters/fields: Blank space denotes lack of information.

Authentication procedures: n/a

 

B. Variable Information

Variable name

Variable definition

Units

Storage type

Range

Missing value codes

Class

The taxonomic class to which the echinoderm belongs

N/A

Character

N/A

N/A

Species

Species used

N/A

Character

N/A

N/A

Depth

Collection depth

N/A

Character

N/A

N/A

Latitude

Geographical latitude of collection

N/A

Numerical

N/A

N/A

Longitude

Geographic longitude of collection

N/A

Numerical

N/A

N/A

Location

Information on where the sample was obtained

N/A

Character

N/A

N/A

Collection method

Information on how the sample was obtained

N/A

Character

N/A

N/A

Skeleton part

Information on the body/skeleton part analyzed

N/A

Character

N/A

N/A

Element concentration (e.g., Ca)

Concentration of the element in ppm or ppb

ppm or ppb

Numerical

N/A

N/A

Ratio (e.g., Li/Ca)

Element/Ca ratio in mmol/mol or µmol/mol

mmol/mol or µmol/mol

Numerical

N/A

N/A

 

C. Graphical and table displays

 Table 1. Echinoderms analyzed for major, minor, and trace elemental geochemistry. Ordered by latitude within class.

Class

Family / Species

n a

Depth (m)

Lat. / Long.

Location

Collection method

Bio-material analyzed b

Asteroidea

Asteriidae / Asterias rubens

5

30

65.81 / -18.09

Eyjafjordur, Iceland (N Atlantic)

Trawling

Whole body

Asteroidea

Asteriidae / Asterias rubens

6

20

65.08 / -22.67

Breidafjordur, Iceland (N Atlantic)

Trawling

Whole body

Asteroidea

Asteriidae / Asterias rubens

10

10

64.04 / -22.06

Straumsvik, Iceland (N Atlantic)

Scuba

Whole body

Asteroidea

Solasteridae / Solaster endeca

4

10

64.04 / -22.06

Straumsvik, Iceland (N Atlantic)

Scuba

Whole body

Asteroidea

Asteriidae / Asterias rubens

8

2

53.24 / -4.46

Swansea (NE Atlantic)

Manual

Whole body

Asteroidea

Asterinidae / Asterina gibbosa

6

2

50.63 / -2.39

English Channel (NE Atlantic)

Manual

Whole body

Asteroidea

Zoroasteridae / Zoroaster fulgens

4

1140

49.28 / -12.36

Porcupine Sea Bight (NE Atlantic)

Semi-otter trawl

Whole body

Asteroidea

Asteriidae / Marthasterias glacialis

7

3

43.58 / -6.24

Cape Vidio (Cantabric Sea)

Manual

Whole body

Asteroidea

Ladidiasteridae / Labidiaster annulatus

9

160–170

-61.21 / -56.01

Elephant Island (Southern Ocean)

Trawling

Arm (plates)

Asteroidea

Astropectinidae / Macroptychaster accrescens

3

140–215

-63.53 / -62.75

Low Island (Southern Ocean)

Trawling

Arm (plates)

Asteroidea

Solasteridae / Paralophaster godfroyi

1

140–215

-63.53 / -62.75

Low Island (Southern Ocean)

Trawling

Arm (plates)

Asteroidea

Solasteridae / Paralophaster sp.

3

140–215

-63.53 / -62.75

Low Island (Southern Ocean)

Trawling

Arm (plates)

Asteroidea

Ganeriidae / Perknaster sp.

2

140–215

-63.53 / -62.75

Low Island (Southern Ocean)

Trawling

Arm (plates)

Asteroidea

Odontasteridae / Acodontaster hodgsoni

3

150–170

-64.15 / -62.74

Dallmann Bay (Southern Ocean)

Trawling

Arm (plates)

Asteroidea

Asterinidae / Kampylaster incurvatus

4

150–170

-64.15 / -62.74

Dallmann Bay (Southern Ocean)

Trawling

Whole body

Asteroidea

Odontasteridae / Odontaster penicillatus

1

150–170

-64.15 / -62.74

Dallmann Bay (Southern Ocean)

Trawling

Arm (plates)

Asteroidea

Poraniidae / Porania antarctica

3

150–170

-64.15 / -62.74

Dallmann Bay (Southern Ocean)

Trawling

Arm (plates)

Asteroidea

Asteriidae / Diplasterias brandti

3

5–40

-64.77 / -64.05

Arthur Harbor (Southern Ocean)

Scuba

Arm (plates)

Asteroidea

Asteriidae / Granaster nutrix

5

5–40

-64.77 / -64.05

Arthur Harbor (Southern Ocean)

Scuba

Whole body

Asteroidea

Asteriidae / Neosmilaster georgianus

3

5–40

-64.77 / -64.05

Arthur Harbor (Southern Ocean)

Scuba

Arm (plates)

Asteroidea

Odontasteridae / Odontaster meridionalis

3

5–40

-64.77 / -64.04

SE Boneparte Pt. (Southern Ocean)

Scuba

Arm (plates)

Asteroidea

Ganeriidae / Perknaster aurorae

3

5–40

-64.78 / -63.99

Stepping Stones (Southern Ocean)

Scuba

Arm (plates)

Asteroidea

Odontasteridae / Acodontaster conspicuus

1

5–40

-65.07 / -63.97

Lemaire Channel (Southern Ocean)

Scuba

Arm (plates)

Asteroidea

Ganeriidae / Perknaster fuscus antracticus

1

5–40

-65.07 / -63.97

Lemaire Channel (Southern Ocean)

Scuba

Arm (plates)

Asteroidea

Echinasteridae / Henricia sp.

2

145–175

-65.67 / -67.40

Renaud Island (Southern Ocean)

Trawling

Arm (plates)

Asteroidea

Pterasteridae / Diplopteraster verrucosus

2

850–950

-66.29 / - 66.60

Banana Trench (Southern Ocean)

Trawling

Arm (plates)

Asteroidea

Odontasteridae / Odontaster validus

6

18

-77.63 / 146.41

Antarctica (Southern Ocean)

ROV

Whole body

Echinoidea

Strongylocentrotidae / Strongylocentrotus droebachiensis

5

30

65.81 / -18.09

Eyjafjordur, Iceland (N Atlantic)

Trawling

Body parts

Echinoidea

Strongylocentrotidae / Strongylocentrotus droebachiensis

5

20

65.08 / -22.67

Breidafjordur, Iceland (N Atlantic)

Trawling

Body parts

Echinoidea

Echinidae / Echinus esculentus

3

20

65.08 / -22.67

Breidafjordur, Iceland (N Atlantic)

Trawling

Body parts

Echinoidea

Echinidae / Echinus esculentus

5

10

64.04 / -22.06

Straumsvik, Iceland (N Atlantic)

Scuba

Body parts

Echinoidea

Strongylocentrotidae / Strongylocentrotus droebachiensis

5

10

64.04 / -22.06

Straumsvik, Iceland (N Atlantic)

Scuba

Body parts

Echinoidea

Parechinidae / Psammechinus miliaris

14

1

50.35 / -4.13

English Channel (NE Atlantic)

Manual

Whole body

Echinoidea

Parechinidae / Paracentrotus lividus

14

2

43.58 / -6.24

Cape Vidio (Cantabric Sea)

Manual

Whole body

Echinoidea

Parechinidae / Paracentrotus lividus

3

1

29.13 / -13.60

Lanzarote (E Atlantic)

Manual

Spines, plates

Echinoidea

Toxopneustidae / Tripneustes ventricosus

2

6

25.12 / -77.29

Paradise Island (W Atlantic)

Manual

Whole body

Echinoidea

Cidaridae / Cidaris blakei

2

595

24.83 / -77.50

South West Reef (W Atlantic)

Submersible

Whole body

Echinoidea

Diadematidae / Diadema setosum

3

0.5

-18.85 / 159.75

Aitukai Island (SW Pacific)

Manual

Spines, plates

Echinoidea

Echinometridae / Evechinus chloroticus

6

5

-45.30 / 166.97

Doubtful Sound (SW Pacific)

Scuba

Spines, plates

Echinoidea

Temnopleuridae / Pseudechinus huttoni

5

8

-45.41 / 167.10

Doubtful Sound (SW Pacific)

Scuba

Spines, plates

Echinoidea

Inc. sed. c / Amphineustes similis

4

670–700

-64.75 / -65.47

Renaud Island (Southern Ocean)

Trawling

Spines, plates

Echinoidea

Cidaridae / Ctenocidaris perrieri

3

670–700

-64.75 / -65.47

Hugo Island (Southern Ocean)

Trawling

Spines, plates

Echinoidea

Echinidae / Sterechinus neumayeri

6

5–40

-65.07 / -63.97

Lemaire Channel (Southern Ocean)

Scuba

Spines, plates

Echinoidea

Echinidae / Sterechinus neumayeri

9

15

-77.06 / 164.42

Antarctica (Southern Ocean)

Scuba

Whole body

Holothuroidea

Holothuriidae / Holothuria forskali

3

3

43.58 / -6.24

Cape Vidio (Cantabric Sea)

Manual

Whole body

Holothuroidea

Molpadiidae / Molpadia musculus

3

670–700

-64.75 / -65.47

Hugo Island (Southern Ocean)

Trawling

Calcareous ring

Holothuroidea

Synallactidae / Pseudostichopus spiculiferus

1

850–950

-66.29 / - 66.60

Banana Trench (Southern Ocean)

Trawling

Calcareous ring

Ophiuroidea

Ophiactidae / Ophiopholis aculeata

11

10

64.04 / -22.06

Straumsvik, Iceland (N Atlantic)

Scuba

Whole body

Ophiuroidea

Ophiolepididae / Ophiosium lynami

6

1140

49.20 / -12.30

Porcupine Sea Bight (NE Atlantic)

Semi-otter trawl

Whole body

Ophiuroidea

Ophiuridae / Ophiura longicauda

3

1

29.12 / -13.56

Lanzarote (E Atlantic)

Manual

Spines, plates

Ophiuroidea

Ophiuridae / Ophionotus victoriae

3

5–40

-64.77 / -64.05

Arthur Harbor (Southern Ocean)

Scuba

Arm (plates)

Ophiuroidea

Ophiacanthidae / Ophiosparte gigas

1

5–40

-64.77 / -64.05

Arthur Harbor (Southern Ocean)

Scuba

Arm (plates)

Crinoidea

Antedonidae / Antedon mediterranea

3

63

41.43 / 2.32

Catalan Sea (Mediterranean Sea)

Benthic trawl

Whole body

a  n number of samples collected from different size classes during field surveys and selected from the literature.
b  This indicates the targeted material for subsequent carbonate ICP-MES analyses. In some cases the whole body with organic matter was not available, thus we used spines, plates, and tests. In the case of starfish arms (Antarctic data), they are representative of the entire body (only as inorganic carbon, thus not comparable to "whole body" data, which include organic material).
c  Inc. sed. is in Latin Incertae sedis and it is used in taxonomy in cases where a species has not been classified or where identify cannot be verified.

Fig1

Fig. 1. Summary of individual element concentration in echinoderm whole body samples to show individual element variability per class. Data reported in ppm (10x, where the x-axis values are the exponent).


 

 

Fig2

Fig. 2. Summary of individual element concentration in echinoderm spines, plates, and calcareous rings (holothurids only) to show individual element variability per class. Data reported in ppm (10x, where the x-axis values are the exponent).


 

Fig3 

Fig. 3. Summary of individual elemental ratios (normalized to Ca2+) in echinoderm whole bodies to show individual element variability per class. Data reported in xmol/mol, where x is milli (m), micro (µ), or nano (n), depending on elemental concentration. The x-axis values are the exponent on 10x.


Fig4 

Fig. 4. Summary of individual elemental ratios (normalized to Ca2+) in echinoderm spines, plates, and calcareous rings (holothurids only) to show individual element variability per class. Data reported in xmol/mol, where x is milli (m), micro (µ), or nano (n), depending on elemental concentration. The x-axis values are the exponent on 10x.


 

TRACE ELEMENTAL CONCENTRATIONS & RATIOS WITH LATITUDE

A. Data Set File

Identity: Full_trace_elemental_concentrations_ratios_latitude_Echinodermata

Size: 91 measurements excluding header rows.

Format and Storage mode: ASCII (comma-delimited), compressed and ZIP

Header information: The first 4 rows of the file name contain the variable names.

Alphanumeric attributes: Mixed

Special characters/fields: Blank space denotes lack of information.

Authentication procedures: n/a

 

B. Variable Information

Variable name

Variable definition

Units

Storage type

Range

Missing value codes

Symbol

The element periodic table symbol and the ratio to Ca (element/Ca)

N/A

Character

N/A

N/A

Element

The element name written in full

N/A

Character

N/A

N/A

Atomic weight

The element atomic weight

N/A

Numerical

N/A

N/A

Units

The element or ratio units in ppm or ppb and mmol/mol or µmol/mol

N/A

Character

N/A

N/A

Detection limit

The analytical detection limit for the element and instrument

N/A

Numerical

N/A

N/A

Whole body

Element concentrations and ratios in whole body samples divided by class and latitude region at large. Data are maximum (max.), minimum (min.), average (avg) and standard deviation (SD)

N/A

Numerical

N/A

N/A

Spines

Element concentrations and ratios in whole body samples divided by class and latitude region at large. Data are maximum (max.), minimum (min.), average (avg) and standard deviation (SD)

N/A

 

Numerical

N/A

N/A

Plates + calcareous ring

Element concentrations and ratios in whole body samples divided by class and latitude region at large. Data are maximum (max.), minimum (min.), average (avg) and standard deviation (SD)

N/A

Numerical

N/A

N/A

 

C. Graphical and table displays

Fig5 

Fig. 5. Individual elemental ratios in echinoderm whole bodies vs. latitude. Data reported in xmol/mol, where x is mili (m), micro (µ), or nano (n), depending on elemental concentration.


 

Fig6

Fig. 6. Individual elemental ratios in echinoderm spines, plates, and calcareous rings (holothuroids only) vs. latitude. Data reported in xmol/mol, where x is mili (m), micro (µ), or nano (n), depending on elemental concentration.


 

Class V. Supplemental descriptors

A. Data acquisition

Data forms: n/a.

Location of completed data forms: n/a

 

B. Quality assurance/quality control procedures:

Data were entered directly from measurements and ratios were computed and converted to the relevant units.

 

C. Computer programs and data processing algorithms:

Maxima, minima, averages and standard deviations were calculated using MS Excel.

D. Archiving: n/a

E. Publications using the data set:

1 manuscript using only the calcium (Ca), magnesium (Mg), and strontium (Sr) data (in review).

Lebrato, M., Ries, J.B., McClintock, J.B., Egilsdottir, H., Lamare, M., Oschlies, A., Dupont, S. and Iglesias-Rodriguez, M.D. in   review. Revisiting the contemporaneous echinoderms global carbonate budget. Earth and Planetary Science Letters.

F. Publications using the same sites: n/a

G. History of data set usage

Data request history: n/a

Data set update history: n/a

Review history: n/a

Questions and comments from secondary users: n/a

Acknowledgments

This work was supported by the "European Project on Ocean Acidification" (EPOCA) for M. Lebrato’s PhD Dissertaion. Work in Antarctica was facilitated by Raytheon Polar Services. Bill Detrich kindly provided ship time for Antarctic collections and samples were identified by C. Mah, R. Mooi, and M. O’Laughlin. The Antarctic collections were supported by NSF awards ANT-0838773 and ANT-1041022 to C.D.A. and J.B.M. J.B.M. acknowledges the support of an endowed professorship in polar and marine biology provided by UAB. JBR acknowledges support from NSF award OCE-1031995 for the elemental analysis of the Arctic specimens.

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