Blooms of Dinoflagellate Mixotrophs in a Lower Chesapeake Bay Tributary: Carbon and Nitrogen Uptake over Diurnal,Seasonal, and Interannual Timescales

A multi-year study was conducted in the eutrophic Lafayette River, a sub-tributary of the lower Chesapeake Bay during which uptake of inorganic and organic nitrogen (N) and C compounds was measured during multiple seasons and years when different dinoflagellate species were dominant. Seasonal dinoflagellate blooms included a variety of mixotrophic dinoflagellates including Heterocapsa triquetra in the late winter, Prorocentrum minimum in the spring, Akashiwo sanguinea in the early summer, and Scrippsiella trochoidea and Cochlodinium polykrikoides in late summer and fall. Results showed that no single N source fueled algal growth, rather rates of N and C uptake varied on seasonal and diurnal timescales, and within blooms as they initiated and developed. Rates of photosynthetic C uptake were low yielding low assimilation numbers during much of the study period and the ability to assimilate dissolved organic carbon augmented photosynthetic C uptake during bloom and non-bloom periods. The ability to use dissolved organic C during the day and night may allow mixotrophic bloom organisms a competitive advantage over co-occurring phytoplankton that are restricted to photoautotrophic growth, obtaining N and C during the day and in well-lit surface waters.     

Changes in dissolved organic matter characteristics in Chincoteague Bay during a bloom of the pelagophyte<Emphasis Type="Italic">Aureococcus anophagefferens</Emphasis>

Aureococcus anophagefferens, the pelagophyte responsible for brown tide blooms, occurs in coastal bays along the northeast coast of the United States. This species was identified in Chincoteague Bay, Maryland, in 1997 and has bloomed there since at least 1998. Time series of dissolved organic matter (DOM) concentrations and characteristics are presented for two sites in Chincoteague Bay: one that experienced a brown tide bloom in 2002 and one that did not. Characteristics of the bulk DOM pool were obtained using dissolved organic carbon (DOC) and ultraviolet-visible (UV-Vis) measurements (spectral slope and specific UV absorbance). High molecular weight DOM (HMW-DOM) was characterized in terms of DOC concentration, carbon: nitrogen (C:N) ratio, isotopic signature, and molecular-level characteristics as determined by direct temperature resolved mass spectrometry (DT-MS). Compositional changes in the DOM pool are associated with brown tide blooms, although a direct relationship between DOM characteristics and bloom development could not be confirmed. DOC measurements suggest that during the brown tide bloom, HMW-DOM was released into the surface water. UV-Vis analysis on the bulk DOM and molecular-level characterization of the HMW-DOM using DT-MS show that this material was optically active and more aromatic in nature. Based upon C:N ratio and HMW-DOC measurements, it appears that this HMW-DOM was more nitrogen enriched. Whether this material was released as exudates or was due to lysis ofA. anophagefferens could not be determined.     

Comparison of Nutrient and Microbial Dynamics over a Seasonal Cycle in a Mid-Atlantic Coastal Lagoon Prone to <Emphasis Type="Italic">Aureococcus anophagefferens</Emphasis> (Brown Tide) Blooms

To determine the roles of dissolved organic matter in the onset, duration, and decline of blooms of the “brown tide” pelagophyte, Aureococcus anophagefferens, nutrient and microbial dynamics, heterotrophic and autotrophic carbon (C) and nitrogen (N) uptake, and peptide hydrolysis were compared in natural populations: (1) seasonally, among physically similar sites in a mid-Atlantic coastal lagoon, Chincoteague Bay, (2) at an individual site as a bloom initiated, developed, and declined, and (3) in whole versus size-fractionated water. Throughout the year, urea was the dominant form of N taken up at both bloom and nonbloom sites. C acquisition in the A. anophagefferens (1.2–5.0 μm) size fraction was dominated by bicarbonate uptake during bloom initiation but organic C compounds were taken up later during and after the bloom. Bacterial productivity was enhanced during and just after the bloom and bacterial abundance was four times higher at the bloom versus nonbloom site.     

Sulfate Reduction and Sulfur Cycles at Two Seagrass Beds Inhabited by Cold Affinity <Emphasis Type="Italic">Zostera marina</Emphasis> and Warm Affinity <Emphasis Type="Italic">Halophila nipponica</Emphasis> in Temperate Coastal Waters

To evaluate the impact of invading seagrass on biogeochemical processes associated with sulfur cycles, we investigated the geochemical properties and sulfate reduction rates (SRRs) in sediments inhabited by invasive warm affinity Halophila nipponica and indigenous cold affinity Zostera marina. A more positive relationship between SRR and below-ground biomass (BGB) was observed at the H. nipponica bed (SRR = 0.6809 × BGB ? 4.3162, r ² = 0.9878, p = 0.0006) than at the Z. marina bed (SRR = 0.3470 × BGB ? 4.0341, r ² = 0.7082, p = 0.0357). These results suggested that SR was more stimulated by the dissolved organic carbon (DOC) exuded from the roots of H. nipponica than by the DOC released from the roots of Z. marina. Despite the enhanced SR in spring-summer, the relatively lower proportion (average, 20%) of acid-volatile sulfur (AVS) in total reduced sulfur and the strong correlation between total oxalate-extractable Fe (Fe_(oxal)) and chromium-reducible sulfur (CRS = 0.2321 × total Fe_(oxal) + 1.8180, r ² = 0.3344, p = 0.0076) in the sediments suggested the rapid re-oxidation of sulfide and precipitation of sulfide with Fe. The turnover rate of the AVS at the H. nipponica bed (0.13 day^?1) was 2.5 times lower than that at the Z. marina bed (0.33 day^?1). Together with lower AVS turnover, the stronger correlation of SRR to BGB in the H. nipponica bed suggests that the extension of H. nipponica resulting from the warming of seawater might provoke more sulfide accumulation in coastal sediments.     

Red Waters of <Emphasis Type="Italic">Myrionecta rubra</Emphasis> are Biogeochemical Hotspots for the Columbia River Estuary with Impacts on Primary/Secondary Productions and Nutrient Cycles

The localized impact of blooms of the mixotrophic ciliate Myrionecta rubra in the Columbia River estuary during 2007–2010 was evaluated with biogeochemical, light microscopy, physiological, and molecular data. M. rubra affected surrounding estuarine nutrient cycles, as indicated by high and low concentrations of organic nutrients and inorganic nitrogen, respectively, associated with red waters. M. rubra blooms also altered the energy transfer pattern in patches of the estuarine water that contain the ciliate by creating areas characterized by high primary production and elevated levels of fresh autochthonous particulate organic matter, therefore shifting the trophic status in emergent red water areas of the estuary from net heterotrophy towards autotrophy. The pelagic estuarine bacterial community structure was unaffected by M. rubra abundance, but red waters of the ciliate do offer a possible link between autotrophic and heterotrophic processes since they were associated with elevated dissolved organic matter and showed a tendency for enhanced microbial secondary production. Taken together, these findings suggest that M. rubra red waters are biogeochemical hotspots of the Columbia River estuary.     

Composition,Abundance, and Life History of Mysids (Crustacea: Mysida) in the Coastal Lagoons of MD,USA

The composition, abundance, biomass, and life history of mysid species were investigated and described for the first time in the Maryland Coastal Bays (38° N, 75° W), Mid-Western Atlantic, using data collected from 2010 to 2013. Three species of mysids were collected, with Neomysis americana being the most abundant species (maximum mean abundance 6.7 ± 6.4 numbers (nos.) m^?2 in July 2013 and biomass 2.78 ± 2.76-mg dry weight (DW) m^?2 in July 2012). Americamysis bahia was the second most abundant species (maximum mean abundance: 0.7 ± 0.4 nos. m^?2 and biomass: 0.23 ± 0.14 mg DW m^?2 in March 2012). Metamysidopsis swifti made up 0.02 to 2 % of mysids and were found in samples collected mainly from southern Chincoteague Bay close to that Bay’s inlet in the fall of 2012. The two most abundant mysid species reproduced continuously from March to July (Neomysis) and May to October (Americamysis). N. americana had larger body and brood sizes than A. bahia. Mysids were relatively low in abundance in late summer, a period of relatively high biomass of fish predators, than during other seasons, suggesting that intense predation might be controlling their abundance. The increase in mysid abundance in the fall following their disappearance in late summer without evidence of reproductive activities suggests species migration from coastal waters into the Maryland Coastal Bays. This annual mysid subsidy perhaps helps to sustain their populations within the bays.     

Variability of Winter-Spring Bloom <Emphasis Type="Italic">Phaeocystis pouchetii</Emphasis> Abundance in Massachusetts Bay

Abundance of the prymnesiophyte Phaeocystis pouchetii was quantified via light microscopy at 2-week to monthly intervals in Massachusetts Bay (southern Gulf of Maine, NW Atlantic) during 1992–2012. Variability in the abundance and seasonal cycle of Phaeocystis are described and synoptic hydrographic, nutrient, and meteorological data were analyzed to identify factors that may influence Phaeocystis abundance. The maximum Phaeocystis abundance was 14?×?10⁶ cells L^?1 (10 Apr 2008). It was frequently (5 of 8 years) absent prior to year 2000, but not thereafter. Seasonally, it first appeared in February to early March, reached peak abundance in mid-April, and persisted until May or early June for a duration of 0–112 days (mean 34 days). A long-term alternation between Phaeocystis and centric diatom abundance was apparent, suggesting winter-spring selection of either Phaeocystis or centric diatoms. Phytoplankton community analysis suggested that blooms affected the rest of the phytoplankton community. Phaeocystis blooms were manifest as a substantial increase in particulate nutrients above normal levels. Phaeocystis blooms were preceded in February by a slightly elevated concentration of NO₃ (9.3 vs. 6.5 μM when absent) and PO₄ (0.99 vs. 0.79 μM when absent). Blooms were also preceded by elevated ratios of NO₃/PO₄, NO₃/Si, and PO₄/Si, and warmer, saltier waters reflecting reduced river discharge. The correlation with salinity and river discharge suggests that Phaeocystis bloom variability is partially determined by annually varying circulation processes that determine the degree of low nutrient, low salinity coastal water intrusion into Massachusetts Bay.     

Biogeochemistry of a River-Dominated Estuary Influenced by Drought and Storms

Increased frequency and severity of droughts, as well as growing human freshwater demands, in the Apalachicola-Chattahoochee-Flint River Basin are expected to lead to a long-term decrease in freshwater discharge to Apalachicola Bay (Florida). To date, no long-term studies have assessed how river discharge variability affects the Bay’s phytoplankton community. Here a 14-year time series was used to assess the influence of hydrologic variability on the biogeochemistry and phytoplankton biomass in Apalachicola Bay. Data were collected at 10 sites in the bay along the salinity gradient and include drought and storm periods. Riverine dissolved inorganic nitrogen and phosphate inputs were correlated to river discharge, but chlorophyll a (Chl a) was similar between periods of drought and average/above-average river discharge in most of the Bay. Results suggest that the potentially negative impact of decreased riverine nutrient input on Bay phytoplankton biomass is mitigated by the nutrient buffering capacity of the estuary. Additionally, increased light availability, longer residence time, and decreased grazing pressures may allow more Chl a biomass to accumulate during drought. In contrast to droughts, tropical cyclones and subsequent increases in river discharge increased flushing and reduced light penetration, leading to reduced Chl a in the Bay. Analysis of the time series revealed that Chl a concentrations in the Bay do not directly mirror the effect of riverine nutrient input, which is masked by multiple interacting mechanisms (i.e., nutrient loading and retention, grazing, flushing, light penetration) that need to be considered when projecting the response of Bay Chl a to changes in freshwater input.     

Impacts of Varying Estuarine Temperature and Light Conditions on <Emphasis Type="Italic">Zostera marina</Emphasis> (Eelgrass) and its Interactions With <Emphasis Type="Italic">Ruppia maritima</Emphasis> (Widgeongrass)

Seagrass populations have been declining globally, with changes attributed to anthropogenic stresses and, more recently, negative effects of global climate change. We examined the distribution of Zostera marina (eelgrass) dominated beds in the York River, Chesapeake Bay, VA over an 8-year time period. Using a temperature-dependent light model, declines in upriver areas were associated with higher light attenuation, resulting in lower light availability relative to compensating light requirements of Z. marina compared with downriver areas. An inverse relationship was observed between SAV growth and temperature with a change between net bed cover increases and decreases for the period of 2004–2011 observed at approximately 23 °C. Z. marina-dominated beds in the lower river have been recovering from a die-off event in 2005 and experienced another near complete decline in 2010, losing an average of 97 % of coverage of Z. marina from June to October. These 2010 declines were attributed to an early summer heat event in which daily mean water temperatures increased from 25 to 30 °C over a 2-week time period, considerably higher than previous years when complete die-offs were not observed. Z. marina recovery from this event was minimal, while Ruppia maritima (widgeongrass) expanded its abundance. Water temperatures are projected to continue to increase in the Chesapeake Bay and elsewhere. These results suggest that short-term exposures to rapidly increasing temperatures by 4–5 °C above normal during summer months can result in widespread diebacks that may lead to Z. marina extirpation from historically vegetated areas, with the potential replacement by other species.     

Effects of common reed (<Emphasis Type="Italic">Phragmites australis</Emphasis>) expansions on nitrogen dynamics of tidal marshes of the northeastern U.S.

Several recent studies indicate that the replacement of extant species withPhragmites australis can alter the size of nitrogen (N) pools and fluxes within tidal marshes. Some common effects ofP. australis expansion are increased standing stocks of N, greater differentiation of N concentrations between plant tissues (high N leaves and low N stems), and slower whole-plant decay rates than competing species (e.g.,Spartina, Typha spp.). Some of the greater differences between marsh types involveP. australis effects on extractable and porewater pools of dissolved inorganic nitrogen (DIN) and N mineralization rates. Brackish and salt marshes show higher concentrations of DIN in porewater beneathSpartina spp. relative toP. australis, but this is not observed in freshwater tidal marshes whenP. australis is compared withTypha spp. or mixed plant assemblages. With few studies of concurrent N fluxes, the net effect ofP. australis on marsh N budgets is difficult to quantify for single sites and even more so between sites. The magnitude and direction of impacts ofP. australis on N cycles appears to be system-specific, driven more by the system and species being invaded than byP. australis itself. WhereP. australis is found to affect N pools and fluxes, we suggest these alterations result from increased biomass (both aboveground and belowground) and increased allocation of that biomass to recalcitrant stems. Because N pools are commonly greater inP. australis than in most other communities (due to plant and litter uptake), one of the most critical questions remaining is “From where is the extra N inP. australis communities coming?” It is important to determine if the source of the new N is imported (e.g., anthropogenic) or internallyproduced (e.g., fixed, remineralized organic matter). In order to estimate net impacts ofP. australis on marsh N budgets, we suggest that further research be focused on the N source that supports high standing stocks of N inP. australis biomass (external input versus internal cycling) and the relative rates of N loss from different marshes (burial versus subsurface flow versus denitrification).     

Influence of Organic Enrichment and <Emphasis Type="Italic">Spisula subtruncata</Emphasis> (da Costa, 1778) on Oxygen and Nutrient Fluxes in Fine Sand Sediments

The role of labile organic material and macrofaunal activity in benthic respiration and nutrient regeneration have been tested in sublittoral fine sand sediments from the Gulf of Valencia (northwestern Mediterranean Sea). Three experimental setups were made using benthic chambers. One experiment was performed in-situ through the annual cycle in a well-sorted fine sand community. The remaining experiments were carried out with mesocosms under laboratory conditions: one with different concentrations of organic enrichment (mussel meat and concentrated diatoms culture), and the other adding two different densities of the endofaunal bivalve Spisula subtruncata. Biochemical variables in surface sediment and changes in oxygen consumption and nutrient fluxes throughout incubation period were studied in each experiment. In the in situ incubations, dissolved oxygen (DO) fluxes showed a strong correlation with sedimentary biopolymeric fraction of organic carbon. Organic enrichment in the laboratory experiments was responsible for increased benthic respiration. However, sediment response (expressed as DO uptake and dissolved inorganic nitrogen—DIN—release) between oligotrophic and eutrophic conditions was more intense than between eutrophic and hypertrophic conditions. S. subtruncata abundances close to 400 and 850 ind m^?2 also intensified benthic metabolism. DO uptake and DIN production in mesocosms with added fauna were between 60 and 75 % and 65–100 % higher than in the control treatment respectively. The results of these three experiments suggest that the macrobenthic community may increase the benthic respiration by roughly a factor of two in these bottoms, where S. subtruncata is one of the dominant species. Both organic enrichment and macrobenthic community in general, and S. subtruncata in particular, did not seem to have a relevant role in P and Si cycles in these sediments.     

Spatial and Temporal Variations in <Emphasis Type="Italic">Pyrodinium bahamense</Emphasis> Cyst Concentrations in the Sediments of Bioluminescent Mangrove Lagoon,St. Croix,USVI

Mangrove Lagoon, located on the island of St. Croix, US Virgin Islands (USVI), is one of few actively bioluminescent lagoons in a location experiencing significant anthropogenic impacts. The bioluminescence is due to an abundance of the dinoflagellate Pyrodinium bahamense in the water column. We recovered surface sediments and sediment cores from Mangrove Lagoon to analyze the spatial distribution and temporal variability of P. bahamense cysts in this system. Surface sediment P. bahamense cyst concentrations ranged from 0 to 466 cysts g^?1 dry sediment, with higher abundances associated with elevated surface water nutrient concentrations and a mixed terrestrial–marine organic matter source regime. In combination with available bioassay data, we hypothesize that phytoplankton utilize nutrients rapidly and subsequent decay of organic matter makes nutrients available for dinoflagellates at the sediment–water interface in the eastern and northern quadrants of the lagoon. However, the nutrients are rapidly exhausted during counterclockwise lagoon circulation resulting in the decline of primary productivity and dinoflagellate abundance in the western quadrants. Downcore profiles suggest that P. bahamense blooms have been occurring for decades, declining in recent years. No cysts were present in sediments predating dredging activities of the 1960s that created Mangrove Lagoon. Recent reductions in cyst abundance may be the result of limited primary productivity caused by restricted water exchange with Salt River Bay due to shallowing of a sill at the mouth of the lagoon. This research highlights the need for more comprehensive geochemical and fossil analyses to better understand long-term ecological variability and inform conservation efforts of these unique habitats.     

Environmental changes and carbon cycle perturbations at the Triassic–Jurassic boundary in northern Switzerland

The Triassic–Jurassic boundary is characterized by strong perturbations of the global carbon cycle, triggered by massive volcanic eruptions related to the onset of the Central Atlantic Magmatic Province. These perturbations are recorded by negative carbon isotope excursions (CIEs) which have been reported worldwide. In this study, Triassic–Jurassic boundary sections from the southern margin of the Central European Basin (CEB) located in northern Switzerland are analyzed for organic carbon and nitrogen isotopes in combination with particulate organic matter (POM) analyses. We reconstruct the evolution of the depositional environment from Late Triassic to Early Jurassic in northern Switzerland and show that observed negative shifts in δ¹³C of the total organic carbon (δ¹³C_TOC) in the sediment are only subordinately influenced by varying organic matter (OM) composition and primarily reflect global changes in the carbon cycle. Based on palynology and the stratigraphic positions of isotopic shifts, the δ¹³C_TOC record of the studied sections is correlated with the GSSP section at Kuhjoch (Tethyan realm) in Austria and with the St. Audrie’s Bay section (CEB realm) in southwest England. We also show that in contrast to POM analyses the applicability of organic carbon/total nitrogen (OC/TN) atomic ratios and stable isotopes of total nitrogen (δ¹⁵N_TN) for detecting changes in source of OM is limited in marginal depositional environments with frequent changes in lithology and OM contents.     

Synthesis,TEM characterization and thermal behaviour of LiNiSi<Subscript>2</Subscript>O<Subscript>6</Subscript> pyroxene

A pyroxene with composition LiNiSi₂O₆ was synthesized at T = 1,473 K and P = 2.0 GPa; the cell parameters at T = 298 K are a = 9.4169(6) Å, b = 8.4465(7) Å, c = 5.2464(3) Å, β = 110.534(6)°, V = 390.78(3) Å³. TEM examination of the LiNiSi₂O₆ pyroxene showed the presence of h + k odd reflections indicative of a primitive lattice, and of antiphase domains obtained by dark field imaging of the h + k odd reflections. A HT in situ investigation was performed by examining TEM selected area diffraction patterns collected at high temperature and synchrotron radiation powder diffraction. In HTTEM the LiNiSi₂O₆ was examined together with LiCrSi₂O₆ pyroxene. In LiCrSi₂O₆ the h + k odd critical reflections disappear at about 340 K; they are sharp up to the transition temperature and do not change their shape until they disappear. In LiNiSi₂O₆ the h + k odd reflections are present up to sample deterioration at 650 K. A high temperature synchrotron radiation powder diffraction investigation was performed on LiNiSi₂O₆ between 298 and 773 K. The analysis of critical reflections and of changes in cell parameters shows that the space group is P-centred up to the highest temperature. The comparative analysis of the thermal and spontaneous strain contributions in P2₁/c and C2/c pyroxenes indicates that the high temperature strain in P-LiNiSi₂O₆ is very similar to that due to thermal strain only in C2/c spodumene and that a spontaneous strain contribution related to pre-transition features is not apparent in LiNiSi₂O₆. A different high-temperature behaviour in LiNiSi₂O₆ with respect to other pyroxenes is suggested, possibly in relation with the presence of Jahn–Teller distortion of the M1 polyhedron centred by low-spin Ni³⁺.     

Quantification of photosynthetic inorganic carbon utilisation via a bidirectional stable carbon isotope tracer

The amount of bicarbonate utilised by plants is usually ignored because of limited measurement methods. Accordingly, this study quantified the photosynthetic assimilation of inorganic carbon (CO₂ and HCO₃ ^?) by plants. The net photosynthetic CO₂ assimilation (P _N), the photosynthetic assimilation of CO₂ and bicarbonate (P _N’), the proportion of increased leaf area (f _LA) and the stable carbon isotope composition (δ¹³C) of Orychophragmus violaceus (Ov) and Brassica juncea (Bj) under three bicarbonate levels (5, 10 and 15 mm NaHCO₃) were examined to determine the relationship among P _N, P _N’ and f _LA. P _N’, not P _N, changed synchronously with f _LA. Moreover, the proportions of exogenous bicarbonate and total bicarbonate (including exogenous bicarbonate and dissolved CO₂-generated bicarbonate) utilised by Ov were 2.27 % and 5.28 % at 5 mm bicarbonate, 7.06 % and 13.28 % at 10 mm bicarbonate, and 8.55 % and 17.31 % at 15 mm bicarbonate, respectively. Meanwhile, the proportions of exogenous bicarbonate and total bicarbonate utilised by Bj were 1.77 % and 3.28 % at 5 mm bicarbonate, 2.11 % and 3.10 % at 10 mm bicarbonate, and 2.36 % and 3.09 % at 15 mm bicarbonate, respectively. Therefore, the dissolved CO₂-generated bicarbonate and exogenous bicarbonate are important sources of inorganic carbon for plants.     

Relationships Between Long-Term Trend of Satellite-Derived Chlorophyll-<Emphasis Type="Italic">a</Emphasis> and Hypoxia Off the Changjiang Estuary

The Changjiang Estuary is one of the largest estuaries in the world, where hypoxia frequently occurs during the summer season. Recent routine surveys in the observed area found that the low dissolved oxygen (DO) in the summer bottom water was not rapidly expanding with increasing nutrient loads in Changjiang diluted waters. Based on the remote sensing data and in situ data, we examined the historic seasonal hypoxia observations for the bottom waters of the Changjiang Estuary and investigated the short- and long-term effects that runoff had on variations in DO and chlorophyll-a (Chl-a). Our analysis indicated that the recent areal variation in hypoxia was due to the changing Chl-a distribution and stratification conditions. The correspondence between hypoxia and surface Chl-a concentration showed that remotely sensed Chl-a larger than 3.0 mg L^?1 was an essential condition for the formation of hypoxia off the Changjiang Estuary. The trend of Chl-a concentration was significantly impacted by the Three Gorges Dam (TGD), and the inter-annual variation of Chl-a was weakly affected by global-scale climate variability. After the TGD impoundment, the sediment loading in the Changjiang runoff and suspended sediments in Changjiang Estuary in August decreased, and the high Chl-a concentration moved landward. These shifted the hypoxia from its optimal forming conditions.     

High-pressure phase transitions of CaRhO<Subscript>3</Subscript> perovskite

High-pressure phase transitions of CaRhO₃ perovskite were examined at pressures of 6–27 GPa and temperatures of 1,000–1,930°C, using a multi-anvil apparatus. The results indicate that CaRhO₃ perovskite successively transforms to two new high-pressure phases with increasing pressure. Rietveld analysis of powder X-ray diffraction data indicated that, in the two new phases, the phase stable at higher pressure possesses the CaIrO₃-type post-perovskite structure (space group Cmcm) with lattice parameters: a = 3.1013(1) Å, b = 9.8555(2) Å, c = 7.2643(1) Å, V _m  = 33.43(1) cm³/mol. The Rietveld analysis also indicated that CaRhO₃ perovskite has the GdFeO₃-type structure (space group Pnma) with lattice parameters: a = 5.5631(1) Å, b = 7.6308(1) Å, c = 5.3267(1) Å, V _m  = 34.04(1) cm³/mol. The third phase stable in the intermediate P, T conditions between perovskite and post-perovskite has monoclinic symmetry with the cell parameters: a = 12.490(3) Å, b = 3.1233(3) Å, c = 8.8630(7) Å, β = 103.96(1)°, V _m  = 33.66(1) cm³/mol (Z = 6). Molar volume changes from perovskite to the intermediate phase and from the intermediate phase to post-perovskite are –1.1 and –0.7%, respectively. The equilibrium phase relations determined indicate that the boundary slopes are large positive values: 29 ± 2 MPa/K for the perovskite—intermediate phase transition and 62 ± 6 MPa/K for the intermediate phase—post-perovskite transition. The structural features of the CaRhO₃ intermediate phase suggest that the phase has edge-sharing RhO₆ octahedra and may have an intermediate structure between perovskite and post-perovskite.     

Stability at high-pressure,elastic behaviour and pressure-induced structural evolution of CsAlSi<Subscript>5</Subscript>O<Subscript>12</Subscript>, a potential host for nuclear waste

The elastic and structural behaviour of the synthetic zeolite CsAlSi₅O₁₂ (a = 16.753(4), b = 13.797(3) and c = 5.0235(17) Å, space group Ama2, Z = 2) were investigated up to 8.5 GPa by in situ single-crystal X-ray diffraction with a diamond anvil cell under hydrostatic conditions. No phase-transition occurs within the P-range investigated. Fitting the volume data with a third-order Birch–Murnaghan equation-of-state gives: V ₀ = 1,155(4) ų, K _T0 = 20(1) GPa and K′ = 6.5(7). The “axial moduli” were calculated with a third-order “linearized” BM-EoS, substituting the cube of the individual lattice parameter (a ³, b ³, c ³) for the volume. The refined axial-EoS parameters are: a ₀ = 16.701(44) Å, K _T0a = 14(2) GPa (β_a = 0.024(3) GPa^?1), K′ _a = 6.2(8) for the a-axis; b ₀ = 13.778(20) Å, K _T0b = 21(3) GPa (β_b = 0.016(2) GPa^?1), K′ _b = 10(2) for the b-axis; c ₀ = 5.018(7) Å, K _T0c = 33(3) GPa (β_c = 0.010(1) GPa^?1), K′ _c = 3.2(8) for the c-axis (K _T0a:K _T0b:K _T0c = 1:1.50:2.36). The HP-crystal structure evolution was studied on the basis of several structural refinements at different pressures: 0.0001 GPa (with crystal in DAC without any pressure medium), 1.58(3), 1.75(4), 1.94(6), 3.25(4), 4.69(5), 7.36(6), 8.45(5) and 0.0001 GPa (after decompression). The main deformation mechanisms at high-pressure are basically driven by tetrahedral tilting, the tetrahedra behaving as rigid-units. A change in the compressional mechanisms was observed at P ≤ 2 GPa. The P-induced structural rearrangement up to 8.5 GPa is completely reversible. The high thermo-elastic stability of CsAlSi₅O_12, the immobility of Cs at HT/HP-conditions, the preservation of crystallinity at least up to 8.5 GPa and 1,000°C in elastic regime and the extremely low leaching rate of Cs from CsAlSi₅O₁₂ allow to consider this open-framework silicate as functional material potentially usable for fixation and deposition of Cs radioisotopes.     

Biodegradation of ortho-dimethyl phthalate by a binary culture of <Emphasis Type="Italic">Variovorax</Emphasis> sp. BS1 and <Emphasis Type="Italic">Achromobacter denitrificans</Emphasis>

Binary mixture of Variovorax sp. BS1 and Achromobacter denitrificans degraded >99 % of 300 mg l^?1 of ortho-dimethyl phthalate (DMP) within 24 h of incubation at 30 °C. Rate of degradation of DMP followed the order: A. denitrificans > binary mixture > Variovorax sp. BS1. Transient intermediate metabolites were not detected using HPLC analyses at any time points using Variovorax sp. BS1 and binary mixture. However, using pure culture of A. denitrificans, monomethyl phthalate was accumulated during the course of DMP biodegradation which disappeared with time of incubation. Binary mixture of Variovorax sp. BS1 and A. denitrificans exhibited better efficiency in terms of biodegradation of DMP as compared to either individual bacterial strain. In addition, fluorescence in situ hybridization technique was used to estimate the population dynamics of Variovorax sp. BS1 in binary mixture. A. denitrificans in mixed culture were estimated by subtracting total number of cells of Variovorax sp. BS1 from the total counts of microbial cells using an epifluorescence microscope after staining with 4′,6-diamidino-2-phenylindole. Results obtained at mid-exponential growth phase suggested the abundance of both bacterial strains as primary degraders.