The marine killers: Dinoflagellates in estaurine and coastal waters

Records of massive fish kills and paralytic shellfish poisoning (PSP) in Europe and North America go back to the 17th century. But, it was not until the 1940s when the relationship between PSP, red tide and toxic dinoflagellateGonyaulax was established. Recent records show that PSP and related poisons caused by toxic dinoflagellates in coastal waters and estuaries, are a world-wide problem. Diarrhetic shellfish poisoning (DSP) and neurotoxic poisoning (NSP), believed earlier as bacterial or viral infections are now shown to be caused by other toxic dinoflagellates such asDinophysis. The shellfish most often involved in the poisoning are mussels and clams. Other dinoflagellates,Gyrodinium, occasionally cause massive fish kills in vast coastal areas, resulting in fishery and economic losses. Factors promoting toxic dinoflagellate bloom development and PSP/DSP outbreaks are not fully understood. In previous studies, temperature was considered as the principal factor influencing dinoflagellate blooming. Recent studies showed that other factors such as salinity, sunlight, freshwater runoff and water stability are also important. Pollution from land drainage and sewage discharge in inshore waters were also implicated. Current knowledge indicates that although chemical and biotic factors are important forin-situ growth of dinoflagellate cells, convergence by thermal and tidal fronts is essential for cell accumulation and bloom development. Advances in physical oceanographic research, modelling and remote sensing enabled the detection of fronts and bordering eddies with high precision. There is a potential for an increased use of these technological advances in predicting and monitoring the bloom development. The present paper overviews the history and distribution of toxic dinoflagellates, and the physical factors influencing bloom development and PSP/DSP outbreaks. Future research needs to improve the predictability and control of this world-wide hazard are also discussed.     

Laguna madre: Seagrass changes continue decades after salinity reduction

Vegetation maps of the lower Laguna Madre prepared from surveys conducted in 1965–1967, 1974–1976, and 1988 document a >330 km² decrease in cover byHalodule wrightii, an increase of almost 190 km² in other seagrass species, and an increase of 140 km² in bare bottom. Loss in seagrass cover is confined to deeper parts of the laguna; turbidity caused by maintenance dredging is the suspected cause. The species shifts are consistent with observed reductions in salinity maxima. Although the hydrological alterations and climatic shift responsible for moderating the salinity regime occurred between 1948 and 1965, the biological changes continue. Establishment of patches away from source meadows appears to be the process for displacing species that limits their rate of expansion into suitable habitat in this elongate embayment.     

Primary production and seasonal aspects of emergent plants in a tidal freshwater marsh

Seasonal changes in aboveground plant biomass, cover, and frequency were monitored in Sweet Hall Marsh, a tidal freshwater marsh located on the Pamunkey River, Virginia, during the 1974 growing season.Peltandra virginica accumulated the most biomass, 423.40 g per m², followed byLeersia oryzoides at 67.75 g per m². Annual net community production was estimated to be 775.74 g per m² by using a multiple-harvest technique. Comparisons with other studies revealed that production was somewhat low for tidal freshwater marshes but mostly higher than production in Virginia brackish and saline wetlands. Measurements revealed an annual succession of plant species from spring to fall. The pattern observed was early dominance byPeltandra followed by a rise in importance ofPolygonum spp.,Impatients capensis andLeersia.     

The abundance and distribution of the toxic dinoflagellate,Gonyaulax tamarensis,in Long Island estuaries

The distribution and abundance of motile cells of the toxic dinoflagellateGonyaulax tamarensis Lebour were monitored in estuarine waters of Long Island, a region with no previous history of shellfish toxicity. The population distribution was patchy, with the species detected in 40% of 115 estuaries examined during the spring bloom season. More detailed studies in four estuaries indicated that the dinoflagellate was most abundant in the headwater regions, with concentrations falling to undetectable levels at the mouths.G. tamarensis cell concentrations did not exceed 10⁵ cells per 1 and often remained an order of magnitude lower. In several instances, population growth and accumulation ceased under seemingly favorable environmental and nutritional conditions.     

The marine killers: Dinoflagellates in estaurine and coastal waters

Records of massive fish kills and paralytic shellfish poisoning (PSP) in Europe and North America go back to the 17th century. But, it was not until the 1940s when the relationship between PSP, red tide and toxic dinoflagellateGonyaulax was established. Recent records show that PSP and related poisons caused by toxic dinoflagellates in coastal waters and estuaries, are a world-wide problem. Diarrhetic shellfish poisoning (DSP) and neurotoxic poisoning (NSP), believed earlier as bacterial or viral infections are now shown to be caused by other toxic dinoflagellates such asDinophysis. The shellfish most often involved in the poisoning are mussels and clams. Other dinoflagellates,Gyrodinium, occasionally cause massive fish kills in vast coastal areas, resulting in fishery and economic losses.Factors promoting toxic dinoflagellate bloom development and PSP/DSP outbreaks are not fully understood. In previous studies, temperature was considered as the principal factor influencing dinoflagellate blooming. Recent studies showed that other factors such as salinity, sunlight, freshwater runoff and water stability are also important. Pollution from land drainage and sewage discharge in inshore waters were also implicated.Current knowledge indicates that although chemical and biotic factors are important forin-situ growth of dinoflagellate cells, convergence by thermal and tidal fronts is essential for cell accumulation and bloom development. Advances in physical oceanographic research, modelling and remote sensing enabled the detection of fronts and bordering eddies with high precision. There is a potential for an increased use of these technological advances in predicting and monitoring the bloom development.The present paper overviews the history and distribution of toxic dinoflagellates, and the physical factors influencing bloom development and PSP/DSP outbreaks. Future research needs to improve the predictability and control of this world-wide hazard are also discussed.     

Macrobenthic communities from wetland impoundments and adjacent open marsh habitats in South Carolina

Forty-eight core and grab samples were taken from two impoundments and an adjacent tidal creek and salt marsh during each of six sampling periods (January, June and November 1983; and January, April and July 1984). Habitats sampled within the impoundments included the perimeter ditch and shallow vegeted areas dominated byRuppia maritima, Spartina alterniflora, andScirpus robustus. The adjacent tidal creek bottom and low marsh ofS. alterniflora were sampled for comparison with the impoundment sites. Major differences in faunal composition and density of macrobenthic invertebrates were observed between habitats in this study. Macrobenthic density was highest (475 individuals 0.05 m^?2) at the impoundment site dominated byScripus robustus, where oligochaetes were abundant. The open marsh site had a density of 254 individuals 0.05 m^?2. Among unvegetated sites, density for all sampling periods was higher in Chainey Creek than in the perimeter ditches of the impoundments. The total number of taxa was highest for the open marsh and tidal creek sites. The impoundments contained vegetated sites which were inhabited by fewer species than nonimpounded sites, while the perimeter ditch sites were comparatively depauperate. Cluster and nodal analyses identified four broad assemblages based on habitat: 1) an open marsh assemblage, 2) a creek assemblage, 3) a eurytopic assemblage, and 4) an impoundment assemblage. The separation of faunal assemblages by sampling site rather than sampling period suggests that physical differences between habitats were important factors determining distribution patterns.     

The effect of shell infestation byPolydora sp. and infection byHaplosporidium nelsoni (MSX) on the tissue condition of oysters,Crassostrea virginica

A number of stressors, including the endoparasiteHaplosporodium nelsoni (MSX), reduce metabolic condition of oysters; however, previous studies of the effect of the shell-boring polychaetePolydora sp. on condition have produced conflicting results. To assess the effects of both symbionts, singly and in combination, we examined 214 oysters for shell infestation byPolydora sp. mud blisters (by image analysis), intensity of infection byH. nelsoni (by histology), and nutritional state (estimated by soft tissue gravimetric condition index). Among all oysters tested, condition index was negatively (p <0.05) correlated withPolydora sp. infestation, although the explained variance (r²) was only about 5%. When oysters withoutH. nelsoni were considered alone, the variance explained byPolydora sp. rose to approximately 30%, indicating that the presence of one deleterious symbiont can confound the effect of another. In oysters withoutH. nelsoni, a 36% loss in tissue condition was associated withPolydora sp. blister infestation covering 45% of the shell. After a single season's exposure to both symbionts, oysters withH. nelsoni had significantly (p<0.05) greaterPolydora sp. infestation than did animals withoutH. nelsoni, but the difference disappeared after a second year, when nearly all shells were infested. The mean condition index for oysters with bothPolydora sp. andH. nelsoni was 13% lower than that for individuals with neither; oysters with only one symbiont had intermediate values. The interaction between percent blister coverage andH. nelsoni intensity on tissue condition was significant (p<0.002), verifying that the effect of the two symbionts was not additive. We conclude thatPolydora sp. reduces the ability of oysters to accumulate nutritional reserves, but that this effect may be obscured by other deleterious influences.     

Effects of nitrogen addition and salt grass (Distichlis spicata) upon high salt marsh vegetation in Northern California, USA

In the salt marshes of Tomales Bay, California, where grazing by cattle increases the input of nitrogen to the marsh (either directly or indirectly as runoff from within the salt marsh watershed), high salt marsh vegetation is dominated byDistichlis spicata and is less diverse than marshes without excess nutrients. Using a field experiment, I investigated the role of soil fertility on the plant community of the high salt marsh. I hypothesized that when soil fertility is increased by nitrogen addition plant productivity will increase, as indicated by height, biomass, and cover, and competitive exclusion, byD. spicata, will lead to a reduction in species richness and evenness, especially where the initial density ofDistichlis is high (from transplanting). After two growing seasons, biweekly nitrogen addition to the high salt marsh led to increased plant biomass and cover. Diversity was not reduced, and space preemption byDistichlis-transplants did not confer a competitive advantage. Although the dominant species thrived (e.g.,Salicornia virginica, D. spicata, Triglochin concinna) they did not displace subdominant species and decrease diversity. The vegetation response in this high salt marsh system does not support the hypothesis that as biomass and cover (indicators of productivity) increase in response to increased nitrogen, competitive exclusion will occur and diversity will decrease.     

Seasonal changes in the amphipod fauna ofMicrociona prolifera (Ellis and Solander) (Porifera: Demospongia) and associated sponges in a shallow salt-marsh creek

Between September 1976 and August 1978, samples of four species of sponge,Microciona prolifera (Ellis and Solander),Haliclona loosanoffi Hartman,Lissodendoryx isodictyalis (Carter) andHalichondria bowerbanki Burton, were collected from subtidal shell debris in a North Edisto River, South Carolina saltmarsh creek and associated amphipods identified. Dominant spongicolous amphipods wereColomastix halichondriae Bousfield,Leucothoe spinicarpa (Abildgaard),Corophium simile Shoemaker,Corophium acherusicum Costa,Lembos cf.L. websteri Bate andMelita appendiculata (Say). Densities of amphipods inMicroclona prolifera andHalichondria bowerbanki usually exceeded those inLissodendoryx isodictyalis andHaliclona loosanoffi. Seasonal changes in amphipod dominance were however approximately the same in all sponge species. Winter dominance byCorophium spp., and on occasionLembos spp., is followed by spring dominance byMelita appendiculata and summer dominance byColomastix halichondriae. Harsher winter conditions in 1976–77 apparently resulted in more reduced populations of various sponge species as well asColomastix halichondriae andLeucothoe spinicarpa when compared with the following winter. With some exceptions during the winter, amphipod density inMicrociona prolifera generally decreased as sponge size increased. The range of gammarid amphipod densities inMicrociona prolifera was 128–724 individuals per 5 g (40.3 cm³) of sponge.     

A large epeiric methanogenic Bambuí sea in the core of Gondwana supercontinent?

Carbon isotope compositions of both sedimentary carbonate and organic matter can be used as key proxies of the global carbon cycle and of its evolution through time,as long as they are acquired from waters where the dissolved inorganic carbon(DIC)is in isotope equilibrium with the atmospheric CO2.However,in shallow water platforms and epeiric settings,the influence of local to regional parameters on carbon cycling may lead to DIG isotope variations unrelated to the global carbon cycle.This may be especially true for the terminal Neoproterozoic,when Gondwana assembly isolated waters masses from the global ocean,and extreme positive and negative carbon isotope excursions are recorded,potentially decoupled from global signals.To improve our understanding on the type of information recorded by these excursions,we investigate the pairedδ^13Ccarb andδ^13Corg evolution for an increasingly restricted late Ediacaran-Cambrian foreland system in the West Gondwana interior:the basal Bambui Group.This succession represents a 1~(st)-order sedimentary sequence and records two majorδ^13Ccarb excursions in its two lowermost lower-rank sequences.The basal cap carbonate interval at the base of the first sequence,deposited when the basin was connected to the ocean,hosts antithetical negative and positive excursions forδ^13Ccarb andδ^13Corg,respectively,resulting inΔ^13C values lower than 25‰.From the top of the basal sequence upwards,an extremely positiveδ^13Ccarb excursion is coupled toδ^13Corg,reaching values of+14‰and-14‰,respectively.This positive excursion represents a remarkable basin-wide carbon isotope feature of the Bambui Group that occurs with only minor changes inΔ^13C values,suggesting change in the DIC isotope composition.We argue that this regional isotopic excursion is related to a disconnection between the intrabasinal and the global carbon cycles.This extreme carbon isotope excursion may have been a product of a disequilibria between the basin DIC and atmospheric CO2 induced by an active methanogenesis,favored by the basin restriction.The drawdown of sulfate reservoir by microbial sulfate reduction in a poorly ventilated and dominantly anoxic basin would have triggered methanogenesis and ultimately methane escape to the atmosphere,resulting in a^13C-enriched DIC influenced by methanogenic CO2.Isolated basins in the interior of the Gondwana supercontinent may have represented a significant source of methane inputs to the atmosphere,potentially affecting both the global carbon cycle and the climate.     

Temperature dependence of the 57Fe Mössbauer parameters in riebeckite

Mössbauer spectra for two riebeckite minerals were collected at temperatures in the range 4.2 to 500 K. The magnetic-ordering temperatures were found to be 33±1 and 31±1 K respectively. Fitting the paramagnetic spectra with a discrete number of doublets (three or four) did not lead to consistent results. Instead, a superposition of an Fe³⁺ (M2) doublet and one distributed ferrous component was found to produce adequate fits with reasonable parameter values. For both samples, a minor fraction of ferrous ions was observed to be present at the M4 sites and for one of the samples at the M2 sites as well. The temperature variations of the center shifts were well reproduced using the Debye model of the lattice vibrational spectrum to evaluate the second-order Doppler shift. The characteristic Mössbauer temperatures were calculated to be in the range 340–390 K for Fe²⁺, and 520 K for Fe³⁺. The temperature dependences of the various ferrous quadrupole splittings could not be explained in terms of the point-charge model and assuming a temperature-independent energy-level scheme for the ⁵D term. It is suggested that a gradual change with temperature of the orbital-level splittings takes place. All calculations yielded a positive sign for the principal component of the electric field gradient (EFG). The spectrum recorded at 4.2 K for one of the riebeckites was fitted with a superposition of an Fe³⁺ and a Fe²⁺ hyperfine-field distribution, the latter one primarily characterizing the Fe²⁺ (M1) cations. The following relevant hyperfine data were calculated: H _hf=161 kOe, ΔE _Q=3.11 mm/s, and V _zz<0, all referring to the maximum-propability values. For the second riebeckite at 4.2 K, an additional distributed ferrous component could independently be resolved. The two maximum-probability hyperfine fields were found to be 189 and 98 kOe and the corresponding ΔE _Q values 3.10 and 2.67 mm/s. Both components exhibit a negative V _zz. The subspectra were attributed to M1 and M3 sites respectively. The Fe³⁺ hyperfine fields are 548+-2 kOe for both riebeckites. The different values found for the Fe³⁺ quadrupole shift 2?_Q for the two samples is explained by a different angle between the hyperfine field and the EFG's principal axis. The magnetic spectra recorded at 15 K and higher, could not be reproduced adequately with reasonable parameter values.     

Isotopic composition of cellulose from aquatic organisms

The stable isotopic ratios of oxygen, carbon and the non-exchangeable carbon-bound hydrogen of cellulose from marine plants (algae and higher vascular forms) and animals (tunicates) collected in their natural habitats and from freshwater vascular plants grown in the laboratory under controlled conditions were determined.The δ¹⁸Ovalues of cellulose from all the plants and animals were 27 ±3% more positive than the δ¹⁸O values of the waters in which the organisms grew. Temperature had little or no influence on this relationship for three species of freshwater vascular plants that were analyzed. The relationship between the δ¹⁸O values of cellulose and the water used in its synthesis is probably established by the isotopic fractionation that occurs during the hydration of carbonyl groups of the intermediates involved in cellulose synthesis.The δD values of the non-exchangeable hydrogen of cellulose (determined by analyzing cellulose nitrate) from different organisms that grew in the same environment differed by large amounts. This difference ranged up to 200‰ for different species of algae collected at a single site: the corresponding difference for different species of tunicates and vascular plants was 60 and 20‰ respectively. The δD values of cellulose nitrate from different species of freshwater vascular plants grown in water of constant temperature and isotopic composition differed by as much as 60‰ The relationship between the δD values of the carbon-bound hydrogen of cellulose and the water used in its synthesis displayed a significant temperature dependence for four species of freshwater vascular plants that were analyzed. The δD values of cellulose nitrate prepared from different parts of one of the plants grown under constant conditions differed by 40‰ Hydrogen isotopic fractionation during cellulose synthesis appears to be more variable among different species and displays a larger temperature dependence than was suggested by previous studies.     

Aspartic acid racemization dating of Holocene brachiopods and bivalves from the southern Brazilian shelf, South Atlantic

The extent of racemization of aspartic acid (Asp) has been used to estimate the ages of 9 shells of the epifaunal calcitic brachiopod Bouchardia rosea and 9 shells of the infaunal aragonitic bivalve Semele casali. Both taxa were collected concurrently from the same sites at depths of 10 m and 30 m off the coast of Brazil. Asp D/L values show an excellent correlation with radiocarbon age at both sites and for both taxa (r²_{Site 9 B. rosea} = 0.97, r²_{Site 1 B. rosea} = 0.997, r²_{Site 9 S. casali} = 0.9998, r²_{Site 1 S. casali} = 0.93). The Asp ratios plotted against reservoir-corrected AMS radiocarbon ages over the time span of multiple millennia can thus be used to develop reliable and precise geochronologies not only for aragonitic mollusks (widely used for dating previously), but also for calcitic brachiopods. At each collection site, Bouchardia specimens display consistently higher D/L values than specimens of Semele. Thermal differences between sites are also notable and in agreement with theoretical expectations, as extents of racemization for both taxa are greater at the warmer, shallower site than at the cooler, deeper one. In late Holocene marine settings, concurrent time series of aragonitic and calcitic shells can be assembled using Asp racemization dating, and parallel multi-centennial to multi-millennial records can be developed simultaneously for multiple biomineral systems.     

Radiation resistant of native Deinococcus spp. isolated from the Lout desert of Iran “the hottest place on Earth”

Two native ionizing radiation-resistant bacteria were isolated and identified from a soil sample collected from extreme conditions of the Lout desert in Iran. The hottest land surface temperature has been recorded in the Lout desert from 2004 to 2009. Also, it is categorized as a hyper arid place. Both ionizing radiation and desiccation may cause damage on genome. Soil sample was irradiated in order to eliminate sensitive bacteria then cultured in one-tenth-strength tryptic soy broth medium. Bacterial suspension used for radiation treatment. Morphological and physiological characterization and phylogenetic studies based on 16S rRNA gene sequence were used for identification. The cells were rod shape, non-motile, non-spore forming and gram positive. The 16S rRNA gene sequence showed 99.5 % of similarity to Deinococcus ficus. Phylogenetic dendrogram demonstrated that the isolates branched with D. xibeiensis, D. ficus and D. mumbaiensis. Both isolates were resistant to >15 kGy of gamma radiation and >600 J m² of UV radiation. This is the first report on radiation resistant bacteria belonging to genus Deinococcus isolated from the Lout desert of Iran.     

Nickel speciation in Sebertia acuminata,a plant growing on a lateritic soil of New Caledonia

Nickel speciation in a nickel hyperaccumulating plant (Sebertia acuminata) and its associated soil of southern New Caledonia was studied using various analytical methods. The soil is formed of iron oxides (goethite, hematite), which contain almost all the nickel. The available nickel is probably linked to the organic matter in the litter. Sebertia acuminata, acts as a nickel pump, and concentrates the metal in its leaves. It partitions nickel and silica; nickel is concentrated in the cells (probably in the vacuoles) as organometallic complexes, whereas silica forms the framework of the cells, and the phytolithes. A thorough study of these plants seems essential in order to define the soil–plant relations, and to propose appropriate ways for ecological restoration. To cite this article: N. Perrier et al., C. R. Geoscience 336 (2004).     

Equation of state of hexagonal aluminous phase in basaltic composition to 63 GPa at 300 K

A laser-heated diamond-anvil cell that is capable of operating up to a pressure of 63 GPa, with X-ray diffraction facilities using a synchrotron radiation source at the SPring-8, has been developed to observe the compressibility of a hexagonal aluminous phase, [K_0.15Na_1.66Ca_0.11Mg_1.29Fe²⁺ _0.86Al_3.13Ti_0.09Si_1.98] _Σ9.27O₁₂. The hexagonal aluminous phase is a potassium host mineral from the subducted oceanic crust in the Earth's lower mantle. A sample was heated using a YAG laser at each pressure increment to relax the deviatoric stress in the sample. X-ray diffraction measurements were carried out at 300 K using an angle-dispersive technique. Pressure was measured using an internal platinum pressure calibrant. The observed unit-cell volumes were used to obtain a third-order Birch–Murnaghan equation of state: unit-cell volume V _o=185.94(±16) ų, density ρ _o=4.145 g/cm³, and bulk modulus K _o=198(±3) GPa when the first pressure is derivative of the bulk modulus K ^′ _o is fixed to 4. The density of hexagonal aluminous phase is lower than that of coexisting Mg-perovskite in the subducted oceanic crust.     

Deuterium and oxygen 18 in precipitation and atmospheric moisture in the upper Urumqi River Basin, eastern Tianshan Mountains

The contribution of stable isotopes in meteorological, climatological and hydrological research is well known. This study analyzed the deuterium and oxygen 18 contents (δD and δ¹⁸O) of precipitation in event-based samples at three stations (Glacier No. 1, Zongkong, Houxia) along the upper Urumqi River Basin from May 2006 to August 2007. The δ¹⁸O in precipitation revealed a wide range and a distinct seasonal variation at all three stations, with enriched values occurring in summer and depleted values in winter. A statistically significant positive correlation was observed between the δ¹⁸O and δD and local surface air temperature, and better linear relationship existed between δ¹⁸O and air temperature than that of δD. This suggests that paleoclimatic archives relating to precipitation δ¹⁸O and δD can be useful for qualitative temperature reconstruction. The d-excess in precipitation also exhibited a seasonal variability. Based on NCEP/NCAR reanalysis data, three-dimensional isentropic back-trajectories in HYSPLIT model were employed to determine the moisture source for each precipitation event. Results indicate a dominant effect of westerly air masses in summer and the integrated influence of westerly and polar air masses in winter, and d-excess can be used as a sensitive tracer of the moisture transport history.     

Magnetic properties of sheet silicates; 2:1 layer minerals

Susceptibility, magnetisation and Mössbauer measurements are reported for a representative selection of 2:1 layer phyllosilicates. Eight samples from the mica, vermiculite and smectite groups include examples diluted in iron which are paramagnetic at all temperatures, as well as iron-rich silicates which order magnetically below 10 K. Anisotropic susceptibility of crystals of muscovite, biotite and vermiculite is quantitatively explained with a model where the Fe²⁺ ions lie in sites of effective trigonal symmetry, the trigonal axis lying normal to the sheets. The ferrous ground state is an orbital singlet. Ferric iron gives an isotropic contribution to the susceptibility. Fe²⁺-Fe²⁺ exchange interactions are ferromagnetic with y ～ 2 K, whereas Fe³⁺-Fe³⁺ coupling is antiferromagnetic in the purely ferric minerals. A positive paramagnetic Curie temperature for glauconite may be attributable to Fe²⁺ → Fe³⁺ charge transfer. Magnetic order was found to set in inhomogeneously for glauconite at 1–7 K. One biotite sample showed an antiferromagnetic transition at T _N =7 K marked by a well-defined susceptibility maximum. Its magnetic structure, consisting of ferromagnetic sheets with moments in their planes coupled antiferromagnetically by other, weak interactions, resembles that found earlier for the 1:1 mineral greenalite.     

Regional and temporal variations in CO2/He,He/He and δC along the North Anatolian Fault Zone,Turkey

New He and C relative abundance, isotope and concentration results from nine geothermal locations situated along an 800-km transect of the North Anatolian Fault Zone (NAFZ), Turkey, that were monitored during the period November 2001–November 2004, are reported. The geothermal waters were collected every 3–6 months to study possible links between temporal geochemical variations and seismic activity along the NAFZ. At the nine sample locations, the He isotope ratios range from 0.24 to 2.3R_A, δ¹³C values range from −4.5 to +5.8‰, and CO₂/³He ratios range from 5 × 10⁹ to 5 × 10¹⁴. The following geochemical observations are noted: (1) the highest ³He/⁴He ratios are found near the Galatean volcanic region, in the central section of the NAFZ, (2) at each of the nine sample locations, the ³He/⁴He ratios are generally constant; however, CO₂/³He ratios and He contents both show one order of magnitude variability, and δ¹³C values show up to ∼4‰ variability, and (3) at all locations (except Re?adiye), δ¹³C values show positive correlations with CO₂ contents. The results indicate that at least three processes are necessary to account for the geochemical variations: (1) binary mixing between crustal and mantle-derived volatiles can explain the general characteristics of ³He/⁴He ratios, δ¹³C values, and CO₂/³He ratios at the nine sample locations; (2) preferential degassing of He from the geothermal waters is responsible for variations in CO₂/³He values and He contents at each sample location; and (3) CO₂ dissolution followed by calcite precipitation is responsible for variations in CO₂ contents and δ¹³C values at most locations. For each of the geochemical parameters, anomalies are defined in the temporal record by values that fall outside two standard deviations of average values at each specific location. Geochemical anomalies that may be related to seismic activity are recorded on June 28, 2004 at Yalova, where a M = 4.2 earthquake occurred 43 days earlier at 15 km distance from the sample location, and on April 7, 2003 at Efteni, where a M = 4.0 earthquake occurred 44 days later at a distance of 12 km. At both locations, the sampling periods containing geochemical anomalies were preceded by an increase in M ? 3 earthquakes occurring within 60 days and less than 40 km distance.     

The influence of artificial radiation damage and thermal annealing on helium diffusion kinetics in apatite

Recent work [Shuster D. L., Flowers R. M. and Farley K. A. (2006) The influence of natural radiation damage on helium diffusion kinetics in apatite. Earth Planet. Sci. Lett.249(3-4), 148-161] revealing a correlation between radiogenic ⁴He concentration and He diffusivity in natural apatites suggests that helium migration is retarded by radiation-induced damage to the crystal structure. If so, the He diffusion kinetics of an apatite is an evolving function of time and the effective uranium concentration in a cooling sample, a fact which must be considered when interpreting apatite (U-Th)/He ages. Here we report the results of experiments designed to investigate and quantify this phenomenon by determining He diffusivities in apatites after systematically adding or removing radiation damage.Radiation damage was added to a suite of synthetic and natural apatites by exposure to between 1 and 100 h of neutron irradiation in a nuclear reactor. The samples were then irradiated with a 220 MeV proton beam and the resulting spallogenic ³He used as a diffusant in step-heating diffusion experiments. In every sample, irradiation increased the activation energy (E_a) and the frequency factor (D_o/a²) of diffusion and yielded a higher He closure temperature (T_c) than the starting material. For example, 100 h in the reactor caused the He closure temperature to increase by as much as 36 °C. For a given neutron fluence the magnitude of increase in closure temperature scales negatively with the initial closure temperature. This is consistent with a logarithmic response in which the neutron damage is additive to the initial damage present. In detail, the irradiations introduce correlated increases in E_a and ln(D_o/a²) that lie on the same array as found in natural apatites. This strongly suggests that neutron-induced damage mimics the damage produced by U and Th decay in natural apatites.To investigate the potential consequences of annealing of radiation damage, samples of Durango apatite were heated in vacuum to temperatures up to 550 °C for between 1 and 350 h. After this treatment the samples were step-heated using the remaining natural ⁴He as the diffusant. At temperatures above 290 °C a systematic change in T_c was observed, with values becoming lower with increasing temperature and time. For example, reduction of T_c from the starting value of 71 to ∼52 °C occurred in 1 h at 375 °C or 10 h at 330 °C. The observed variations in T_c are strongly correlated with the fission track length reduction predicted from the initial holding time and temperature. Furthermore, like the neutron irradiated apatites, these samples plot on the same E_a − ln(D_o/a²) array as natural samples, suggesting that damage annealing is simply undoing the consequences of damage accumulation in terms of He diffusivity.Taken together these data provide unequivocal evidence that at these levels, radiation damage acts to retard He diffusion in apatite, and that thermal annealing reverses the process. The data provide support for the previously described radiation damage trapping kinetic model of Shuster et al. (2006) and can be used to define a model which fully accommodates damage production and annealing.