Atmospheric depositional fluxes of \u3csup\u3e7\u3c/sup\u3eBe and \u3csup\u3e210\u3c/sup\u3ePb at Galveston and College Station, Texas

The bulk depositional fluxes of 210Pb and 7Be were measured at a coastal (Galveston) and an inland (College Station) station for about 3 years, between 1989 and 1991. The annual depositional fluxes of 7Be and 210Pb at Galveston during this period varied by a factor of about 2.5, between 8.9 and 23.2 disintegrations per minute (dpm) cm−2 yr−1, with a mean of 14.7 dpm cm−2 yr−1 for 7Be, and 0.67 and 1.71 dpm cm−2 yr−1, with a mean of 1.03 dpm cm−2 yr−1 for 210Pb, respectively. The precipitation-normalized 7Be flux increases with increasing amount of precipitation. There is no systematic and consistent seasonal trend in the depositional fluxes for 7Be or for 210Pb. The volume-weighted 210Pb concentrations, when normalized to the amount of precipitation, seem to be constant over the time period of this study. Four to six heavy rain events (\u3e 5 cm) in a single day account for 20–30% of the annual deposition of 7Be and 210Pb. Such events account, however, for only about 4–6% of the total number of rainy days in a year. The dry depositional fluxes of these nuclides appear to be a significant fraction of the bulk depositional flux only during the months when there is very little rain. The fraction of dry to total depositional flux of 210Pb appears to be higher than that of 7Be. The strong positive correlation between 7Be and 210Pb depositional fluxes indicates that the flux of both nuclides is controlled by scavenging processes by local precipitation. This correlation also indicates that a major portion of the air masses that brings precipitation to Galveston and College Station is of continental origin. Our data therefore suggest that 7Be and 210Pb cannot be used as independent atmospheric tracers in our coastal station. This observation is consistent with those observed at many other continental and coastal stations

Biogeochemical Cycling and Environmental Stability of Pu Relevant to Long-Term Stewardship of DOE Sites

The overall objective of this proposed research is to understand the biogeochemical cycling of Pu in environments of interest to long-term DOE stewardship issues. Central to Pu cycling (transport initiation to immobilization) is the role of microorganisms. The hypothesis underlying this proposal is that microbial activity is the causative agent in initiating the mobilization of Pu in near-surface environments: through the transformation of Pu associated with solid phases, production of extracellular polymeric substances (EPS) carrier phases, and the creation of microenvironments. Also, microbial processes are central to the immobilization of Pu species, through the metabolism of organically complexed Pu species and Pu associated with extracellular carrier phases and the creation of environments favorable for Pu transport retardation

Molecular Level Characterization of Diatom and Coccolithophore-Associated Biopolymers That Are Binding 210Pb and 210Po in Seawater

Through a combination of selective extractions and molecular characterization techniques including Isoelectric Focusing Chromatography and Electrospray Ionization Fourier-Transform Ion Cyclotron Resonance Mass spectrometry, molecular structures of diatom (Phaeodactylum tricornutum) and coccolithophore (Emiliania huxleyi)-associated biopolymers that are responsible for the distinct partitioning behavior between 210Pb and 210Po were determined. Our results show that diatom-derived biopolymers have distinctive elemental grouping distributions as compared to those excreted by the coccolithophore, with the former consisting of more heterogeneous elements (i.e., nitrogen, sulfur and phosphorus-containing organic compounds). For the coccolithophore culture, two 210Pb-enriched biopolymers (non-attached exopolymeric substances and coccosphere shell-associated biopolymers) have a higher abundance of CHO-type compounds, suggesting CHO-only-type compounds as the main binding moieties for 210Pb. In contrast, such association was not evident in the diatom culture. Different with 210Pb, 210Po enrichment in coccolithophore-derived attached exopolymeric substances and Fe-Mn-associated metabolites coincided with the higher abundance of nitrogen/sulfur-containing organic compounds in these two biopolymer fractions, suggesting the strong parallel of Po with the production of nitrogen-rich organic matter as well as sulfur-containing amino acids. These different associations between 210Pb/210Po and organic functional groups were further explored by separating 210Pb or 210Po-labeled coccolithophore-derived biopolymers via isoelectric focusing. This technique suggests that phosphate group-containing molecules but not the other molecules that contain heterogeneous elements (e.g., CHONS, CHON, and CHOS) as the strongest binding agents for 210Pb, while the more hydrophobic (high protein to carbohydrate ratio) nitrogen/sulfur-enriched organic moieties acted as the main 210Po-binding ligands. It is concluded that the deficiency of 210Po with respect to 210Pb can be influenced by the relative abundance of nitrogen/sulfur-enriched organic moieties to the nitrogen/sulfur-depleted organic compounds in the water column. This behavior constrains the application of 210Po-210Pb approach to quantify the particulate organic carbon (POC) export flux in the ocean. It also explains that differences in chemical binding of the 210Po as compared to those of other radionuclides (e.g., thorium-234) as the main factor. That suggests that differences in decay half-lives or physical factors are less important when these nuclides are applied to estimate the POC flux in the ocean

Relative mobility of radioactive trace elements across the sediment-water interface in the MERL model ecosystems of Narragansett Bay

The mobilities of radioactive trace elements across the water sediment boundary of a coastal marine ecosystem were investigated. The studies carried out included chemical speciation experiments ofthe solution and solid phases, as well as verification experiments in controlled model ecosystems ( MERL tanks). The latter included backdiffusion experiments under oxic and anoxic conditions and experiments with artificially increased sediment resuspension rates. These studies have produced seven general conclusions: (1) The backdiffusion of Cs, Mn, Co, and Zn radiotracers across the sediment-water interface into oxic waters and of Mn and Co radiotracers into anoxic waters was predicted from laboratory experiments. (2) The removal from the water and the partial immobilization in the sediments of Cs, Zn and Cd tracers, during anoxic conditions, agreed with results from selective leaching experiments of surface sediments with dithionite-citrate solution, a mildly reducing agent which can reprecipitate liberated metals as sulfides. While most nuclides were leached by this solution to the same extent as by hydroxylamine, another reducing agent, Zn, Cd and Cs tracers were not, possibly due to the formation of sulfidic and other phases by the former solution. (3) Radioisotopes of particle-reactive elements (Sn, Fe, Hg and Cr) were shown by sequential extraction and ultrafiltration experiments to be involved in the dynamic cycle of colloid formation and aggregation in the water column and sediments. (4) In order to extend the information on nuclide behavior gained from the radiotracer methodology to stable trace elements, (which are often introduced into coastal water in ionic form) stable metals were added to one tank. Radiotracer behavior in the water column (removal rates and extent of uptake by suspended particles) was quite similar to that of their stable metal counterparts at ambient concentrations (Mn, Cr, Fe, Cd and Zn), added simultaneously to one tank, and to the metal behavior in other tanks operating under similar conditions. (5) The experiments with increased resuspension rates without concomitant increased bioturbation rates had, as expected, only small effects on removal rates of the radiotracers. (6) Sediment profiles of the tracers revealed both seasonal and element-specific differences in mobility near the sediment interface. Tracer profiles allowed the calculation of bioturbation (tracer microspheres) and pore water diffusion (22Na) rates, as well as an investigation of the spacial and temporal dynamics of trace element cycling near the sediment-water interface. (7) Se and Cr nuclides which were added in different oxidation states to different tanks, showed that the higher oxidation state forms (Se-VI, Cr-VI) are removed more slowly from the water column than the lower oxidation state forms (Se-IV, Cr-III). Furthermore, speciation experiments have shown that the increase in the colloidal fraction of Se may be used to calculate the characteristic times of Se-reduction to elemental or organically-bound forms

Biogeochemical Cycling and Environmental Stability of Pu Relevant to Long-Term Stewardship of DOE Sites

The overall objective of this proposed research is to understand the biogeochemical cycling of Pu in environments of interest to long-term DOE stewardship issues. Central to Pu cycling (transport initiation to immobilization) is the role of microorganisms. The hypothesis underlying this proposal is that microbial activity is the causative agent in initiating the mobilization of Pu in near-surface environments: through the transformation of Pu associated with solid phases, production of extracellular polymeric substances (EPS) carrier phases, and the creation of microenvironments. Also, microbial processes are central to the immobilization of Pu species, through the metabolism of organically complexed Pu species and Pu associated with extracellular carrier phases and the creation of environments favorable for Pu transport retardation

Molecular Level Characterization of Diatom-Associated Biopolymers that Bind 234Th, ²³³PA, ²¹°Pb, and 7Be in Seawater: A Case Study With Phaeodactylum tricornutum

In order to investigate the importance of biogenic silica associated biopolymers on the scavenging of radionuclides, the diatom Phaeodactylum tricornutum was incubated together with the radionuclides Th-234, Pa-233, Pb-210, and Be-7 during their growth phase. Normalized affinity coefficients were determined for the radionuclides bound with different organic compound classes (i.e., proteins, total carbohydrates, uronic acids) in extracellular (nonattached and attached exopolymeric substances), intracellular (ethylene diamine tetraacetic acid and sodium dodecyl sulfate extractable), and frustule embedded biopolymeric fractions (BF). Results indicated that radionuclides were mostly concentrated in frustule BF. Among three measured organic components, Uronic acids showed the strongest affinities to all tested radionuclides. Confirmed by spectrophotometry and two-dimensional heteronuclear single quantum coherence-nuclear magnetic resonance analyses, the frustule BF were mainly composed of carboxyl-rich, aliphatic-phosphoproteins, which were likely responsible for the strong binding of many of the radionuclides. Results from this study provide evidence for selective absorption of radionuclides with different kinds of diatom-associated biopolymers acting in concert rather than as a single compound. This clearly indicates the importance of these diatom-related biopolymers, especially frustule biopolymers, in the scavenging and fractionation of radionuclides used as particle tracers in the ocean

Intracellular Uptake: A Possible Mechanism for Silver Engineered Nanoparticle Toxicity to a Freshwater Alga Ochromonas danica

The behavior and toxicity of silver engineered nanoparticles (Ag-ENs) to the mixotrophic freshwater alga Ochromonas danica were examined in the present study to determine whether any other mechanisms are involved in their algal toxicity besides Ag+ liberation outside the cells. Despite their good dispersability, the Ag-ENs were found to continuously aggregate and dissolve rapidly. When the initial nanoparticle concentration was lower than 10 µM, the total dissolved Ag+ concentration ([Ag+]T) in the suspending media reached its maximum after 1 d and then decreased suggesting that Ag+ release might be limited by the nanoparticle surface area under these conditions. Furthermore, Ag-EN dissolution extent remarkably increased in the presence of glutathione. In the Ag-EN toxicity experiment, glutathione was also used to eliminate the indirect effects of Ag+ that was released. However, remarkable toxicity was still observed although the free Ag+ concentration in the media was orders of magnitude lower than the non-observed effect concentration of Ag+ itself. Such inhibitive effects were mitigated when more glutathione was added, but could never be completely eliminated. Most importantly, we demonstrate, for the first time, that Ag-ENs can be taken in and accumulated inside the algal cells, where they exerted their toxic effects. Therefore, nanoparticle internalization may be an alternative pathway through which algal growth can be influenced

Methods for analyzing the concentration and speciation of major and trace elements in marine particles

Particles influence trace element and isotope (TEI) cycles through both their elemental composition and fate and their role on the partitioning of dissolved elements through scavenging and dissolution. Because of their complex compositions, a diverse suite of methods is required to analyze marine particles. Here we review some of the varied approaches used to study particle composition, speciation and fate. We focus on high throughput analytical methods that are useful for the international GEOTRACES program, and we also describe new spectroscopic techniques that are now being applied to study the spatial distribution and chemical speciation of TEIs in marine particles