Nanocrystalline and Amorphous Calcium Carbonate from Waste Seashells by Ball Milling Mechanochemistry Processes.

Nanocrystalline calcium carbonate (CaCO3) and amorphous CaCO3 (ACC) are materials of increasing technological interest. Nowadays, they are mainly synthetically produced by wet reactions using CaCO3 reagents in the presence of stabilizers. However, it has recently been discovered that ACC can be produced by ball milling calcite. Calcite and/or aragonite are the mineral phases of mollusk shells, which are formed from ACC precursors. Here, we investigated the possibility to convert, on a potentially industrial scale, the biogenic CaCO3 (bCC) from waste mollusk seashells into nanocrystalline CaCO3 and ACC. Waste seashells from the aquaculture species, namely oysters (Crassostrea gigas, low-Mg calcite), scallops (Pecten jacobaeus, medium-Mg calcite), and clams (Chamelea gallina, aragonite) were used. The ball milling process was carried out by using different dispersing solvents and potential ACC stabilizers. Structural, morphological, and spectroscopic characterization techniques were used. The results showed that the mechanochemical process produced a reduction of the crystalline domain sizes and formation of ACC domains, which coexisted in microsized aggregates. Interestingly, bCC behaved differently from the geogenic CaCO3 (gCC), and upon long milling times (24 h), the ACC reconverted into crystalline phases. The aging in diverse environments of mechanochemically treated bCC produced a mixture of calcite and aragonite in a species-specific mass ratio, while the ACC from gCC converted only into calcite. In conclusion, this research showed that bCC can produce nanocrystalline CaCO3 and ACC composites or mixtures having species-specific features. These materials can enlarge the already wide fields of applications of CaCO3, which span from medical to material science.

Eight years of community structure monitoring through recreational citizen science at the "SS Thistlegorm" wreck (Red Sea).

Large artificial coral reef communities, such as those thriving on sunken shipwrecks, tend to mirror those of nearby natural coral reefs and their long-term dynamics may help future reef resilience to environmental change. We examined the community structure of the world-renown "SS Thistlegorm" wreck in the northern Red Sea from 2007 through 2014, analyzing data collected during the recreational citizen science Red Sea monitoring project "Scuba Tourism for the Environment". Volunteer divers collected data on 6 different diving parameters which included the date of the dive, maximum depth, average depth, temperature, dive time, hour of dive, and gave an abundance estimation of sighted taxa from a list of 72 target taxa. Although yearly variations in community structure were significant, there was no clear temporal trend, and 71 of all 72 target taxa were sighted throughout the 8 years. The 5 main taxa driving variations among year clusters in taxa presence/absence (Soft Tree Coral-Dendronephthya spp., Giant Moray-Gymnothorax javanicus, Squirrel Fish-Sargocentron spp., Humpback Batfish-Platax spp., and Caranxes-Carangidae) and taxa abundance (Soft Tree Coral, Giant Moray, Red Sea Clownfish-Amphiprion bicinctus, Napoleon Wrasse-Cheilinus undulatus, and Caranxes) data were determined. The "SS Thistlegorm" provides a compelling example of how artificial coral reefs can sustain a well-established community structure similar to those of their natural counterparts.

Acclimatization of a coral-dinoflagellate mutualism at a CO2 vent.

Ocean acidification caused by shifts in ocean carbonate chemistry resulting from increased atmospheric CO2 concentrations is threatening many calcifying organisms, including corals. Here we assessed autotrophy vs heterotrophy shifts in the Mediterranean zooxanthellate scleractinian coral Balanophyllia europaea acclimatized to low pH/high pCO2 conditions at a CO2 vent off Panarea Island (Italy). Dinoflagellate endosymbiont densities were higher at lowest pH Sites where changes in the distribution of distinct haplotypes of a host-specific symbiont species, Philozoon balanophyllum, were observed. An increase in symbiont C/N ratios was observed at low pH, likely as a result of increased C fixation by higher symbiont cell densities. δ13C values of the symbionts and host tissue reached similar values at the lowest pH Site, suggesting an increased influence of autotrophy with increasing acidification. Host tissue δ15N values of 0‰ strongly suggest that diazotroph N2 fixation is occurring within the coral tissue/mucus at the low pH Sites, likely explaining the decrease in host tissue C/N ratios with acidification. Overall, our findings show an acclimatization of this coral-dinoflagellate mutualism through trophic adjustment and symbiont haplotype differences with increasing acidification, highlighting that some corals are capable of acclimatizing to ocean acidification predicted under end-of-century scenarios.

Recovering and Exploiting Aragonite and Calcite Single Crystals with Biologically Controlled Shapes from Mussel Shells.

Control over the shape and morphology of single crystals is a theme of great interest in fundamental science and for technological application. Many synthetic strategies to achieve this goal are inspired by biomineralization processes. Indeed, organisms are able to produce crystals with high fidelity in shape and morphology utilizing macromolecules that act as modifiers. An alternative strategy can be the recovery of crystals from biomineralization products, in this case, seashells. In particular, waste mussel shells from aquaculture are considered. They are mainly built up of single crystals of calcite fibers and aragonite tablets forming an outer and an inner layer, respectively. A simple mechanochemical treatment has been developed to separate and recover these two typologies of single crystals. The characterization of these single crystals showed peculiar properties with respect to the calcium carbonate from quarry or synthesis. We exploited these biomaterials in the water remediation field using them as substrate adsorbing dyes. We found that these substrates show a high capability of adsorption for anionic dye, such as Eosin Y, but a low capability of adsorption for cationic dyes, such as Blue Methylene. The adsorption was reversible at pH 5.6. This application represents just an example of the potential use of these biogenic single crystals. We also envision potential applications as reinforcing fillers and optical devices.

Decreasing pH impairs sexual reproduction in a Mediterranean coral transplanted at a CO2 vent.

Ocean acidification, due to the increase of carbon dioxide (CO2) concentration in the atmosphere and its absorption by the oceans, affects many aspects of marine calcifying organisms' biology, including reproduction. Most of the available studies on low pH effects on coral reproduction have been conducted on tropical species under controlled conditions, while little information is reported for either tropical or temperate species in the field. This study describes the influence of decreasing pH on sexual reproduction of the temperate non-zooxanthellate colonial scleractinian Astroides calycularis, transplanted in four sites along a natural pH gradient at the underwater volcanic crater of Panarea Island (Tyrrhenian Sea, Italy). The average pH values of each site (range: pHTS 8.07-7.40) match different scenarios of the Intergovernmental Panel on Climate Change (IPCC) for the end of the century. After 3 months under experimental conditions, the reproductive parameters of both oocytes and spermaries (abundance, gonadal index, and diameters) seem to be unaffected by low pH. However, a delay in spermary development in the pre-fertilization period and a persistence of mature oocytes in the fertilization period were observed in the most acidic site. Furthermore, no embryos were found in colonies from the two most acidic sites, suggesting a delay or an interruption of the fertilization process due to acidified conditions. These findings suggest a negative effect of low pH on A. calycularis sexual reproduction. However, long-term experiments, including the synergistic impact of pH and temperature, are needed to predict if this species will be able to adapt to climate change over the next century.

Reproductive output of a non-zooxanthellate temperate coral is unaffected by temperature along an extended latitudinal gradient.

Global environmental change, in marine ecosystems, is associated with concurrent shifts in water temperature, circulation, stratification, and nutrient input, with potentially wide-ranging biological effects. Variations in seawater temperature might alter physiological functioning, reproductive efficiency, and demographic traits of marine organisms, leading to shifts in population size and abundance. Differences in temperature tolerances between organisms can identify individual and ecological characteristics, which make corals able to persist and adapt in a climate change context. Here we investigated the possible effect of temperature on the reproductive output of the solitary non-zooxanthellate temperate coral Leptopsammia pruvoti, along an 8° latitudinal gradient. Samples have been collected in six populations along the gradient and each polyp was examined using histological and cyto-histometric analyses. We coupled our results with previous studies on the growth, demography, and calcification of L. pruvoti along the same temperature gradient, and compared them with those of another sympatric zooxanthellate coral Balanophyllia europaea to understand which trophic strategy makes the coral more tolerant to increasing temperature. The non-zooxanthellate species seemed to be quite tolerant to temperature increases, probably due to the lack of the symbiosis with zooxanthellae. To our knowledge, this is the first field investigation of the relationship between reproductive output and temperature increase of a temperate asymbiotic coral, providing novel insights into the poorly studied non-zooxanthellate scleractinians.

Population Structure of Montastraea cavernosa on Shallow versus Mesophotic Reefs in Bermuda.

Mesophotic coral reef ecosystems remain largely unexplored with only limited information available on taxonomic composition, abundance and distribution. Yet, mesophotic reefs may serve as potential refugia for shallow-water species and thus understanding biodiversity, ecology and connectivity of deep reef communities is integral for resource management and conservation. The Caribbean coral, Montastraea cavernosa, is considered a depth generalist and is commonly found at mesophotic depths. We surveyed abundance and size-frequency of M. cavernosa populations at six shallow (10m) and six upper mesophotic (45m) sites in Bermuda and found population structure was depth dependent. The mean surface area of colonies at mesophotic sites was significantly smaller than at shallow sites, suggesting that growth rates and maximum colony surface area are limited on mesophotic reefs. Colony density was significantly higher at mesophotic sites, however, resulting in equal contributions to overall percent cover. Size-frequency distributions between shallow and mesophotic sites were also significantly different with populations at mesophotic reefs skewed towards smaller individuals. Overall, the results of this study provide valuable baseline data on population structure, which indicate that the mesophotic reefs of Bermuda support an established population of M. cavernosa.

Annual Reproductive Cycle and Unusual Embryogenesis of a Temperate Coral in the Mediterranean Sea.

The variety of reproductive processes and modes among coral species reflects their extraordinary regeneration ability. Scleractinians are an established example of clonal animals that can exhibit a mixed strategy of sexual and asexual reproduction to maintain their populations. This study provides the first description of the annual reproductive cycle and embryogenesis of the temperate species Caryophyllia inornata. Cytometric analyses were used to define the annual development of germ cells and embryogenesis. The species was gonochoric with three times more male polyps than female. Polyps were sexually mature from 6 to 8 mm length. Not only females, but also sexually inactive individuals (without germ cells) and males were found to brood their embryos. Spermaries required 12 months to reach maturity, while oogenesis seemed to occur more rapidly (5-6 months). Female polyps were found only during spring and summer. Furthermore, the rate of gamete development in both females and males increased significantly from March to May and fertilization was estimated to occur from April to July, when mature germ cells disappeared. Gametogenesis showed a strong seasonal influence, while embryos were found throughout the year in males and in sexually inactive individuals without a defined trend. This unusual embryogenesis suggests the possibility of agamic reproduction, which combined with sexual reproduction results in high fertility. This mechanism is uncommon and only four other scleractinians (Pocillopora damicornis, Tubastraea diaphana, T. coccinea and Oulastrea crispata) have been shown to generate their broods asexually. The precise nature of this process is still unknown.

Unusual pattern of embryogenesis of Caryophyllia inornata (Scleractinia, Caryophylliidae) in the Mediterranean sea: maybe agamic reproduction?

While knowledge of the reproductive biology of tropical scleractinian corals is extensive, information from temperate zones is limited. The aim of this study is to describe the reproductive biology of Caryophyllia inornata, a temperate species, and to increase the understanding of the reproductive strategies of Mediterranean corals. Samples of C. inornata were collected during SCUBA surveys at Elba island. Sexually active individuals displayed either male or female germ cells, showing a gonochoric sexuality. C. inornata exhibited an unusual pattern of embryogenesis. Embryos appeared throughout the whole year in males and in sexually inactive individuals, and they did not show a seasonal pattern of development, as usually expected for sexual reproduction. This observation suggests the possibility of asexual origin. These embryogenetic sexually inactive individuals were larger in size than the embryogenetic sexually active ones, and they might be senile polyps that preserve the ability to produce embryos only by agamic reproduction.

[Relationship between the obstructive sleep apnea syndrome and internal medicine]. / Correlazione tra la sindrome delle apnee notturne di tipo ostruttivo e la medicina interna.

Twelve to twenty-five percent of human population suffer from sleep disorders and sleep-related breathing disorders have a frequency of 5-10%. The association between sleep-related breathing disorders and several diseases, mainly cardiovascular and dysmetabolic, is well known. The aim of this study was to assess the prevalence of this association in a group of 620 patients, aged between 18 and 78 years and referred to the Laboratory of Respiratory Pathophysiology of the Umberto I Hospital of Rome. All patients had a clinical history of a sleep-related breathing disorder and answered a specific questionnaire. One-hundred-and-thirty-seven patients (120 males and 17 females, mean age 64 years), whose questionnaire was suggestive of a sleep-related breathing disorder, underwent clinical assessment including blood tests, lung function tests, blood-gas analysis, ECG and nocturnal polysomnography, either as in- or as out-patients. The main associated pathologies were: arterial hypertension (54.7%), chronic obstructive pulmonary disease (17.9%), obesity (63.1%), dyslipidemia (41%), type 2 diabetes mellitus (6.3%), gastroesophageal reflux (27.3%) and cardiac arrhythmias (4.2%); 95 patients with obstructive sleep apnea syndrome were treated, on the basis of the polysomnography outcomes and according to the Italian Association of Sleep Medicine Guidelines, either with preventive strategies for risk factor reduction, or with medical (positive pressure ventilation, oxygen, assessment of the best drug medication) and/or ear, nose end throat surgical therapies. In most patients, the improvement in the sleep-related breathing disorder was associated with an improvement in their systemic pathology, in particular cardiovascular disease, suggesting the need of a deeper consideration and comprehension of nocturnal apneas.