Effects of ligand speciation on determinations of the complexing abilities of strong ligands in natural waters

The presence of organic ligands (L) whose conditional stability constants (K_ML) are strong enough to allow them to form complexes with copper has been reported in oceanic waters. However, there is no general agreement on the distributional characteristics of such strong ligands in the water column. We present that these inconsistencies are derived from not only different analytical methods employed for their detection but also different oceanographic conditions. In particular, the nature and quantities of detectable natural ligands are affected by what kind of form the ligands are presentin situ in different marine environments, that is, chemical speciation of natural ligands (ligand speciation), which depends strongly on the variations in concentrations of coexisting trace metals. Using published data from observations in the laboratory and the field, we provide limits to the ranges of conditional stability constants of organic ligands for copper, zinc and cadmium that are detectable by the extensively used direct metal-titration method. For example, our model indicates that organic ligands for copper with log K_CuL(Cu)>12.4 in surface water and with log K_CuL(Cu)>9.9 in deep water might not have been detected because stronger ligands had formed complexes with ambient metalsin situ at a station in the North Pacific. The estimation suggests that there is a basinscale difference in speciation of natural organic ligands and, moreover, that this difference influences metal speciation. It is postulated that comparisons of the occurrence and levels of organic ligands might not be possible among spatially and temporally different observations without reconciliation of the effects of speciation of the ligands, even if an identical method is used in every case.     

Determination of the lithium and rubidium in sea water by double channel flame emission spectrophotometry

A precise and accurate technique for the determination of Li and Rb in sea water has been developed by using a double channel flame emission spectrophotometer. The advantage of this technique is that it is possible to correct the background emission by making use of the double channel system of the apparatus and to obtain constant intensity of emission even if there are large scale changes in the salinity of the sample. Sea water samples collected in the open sea and coastal areas of Japan were analyzed by this method. In one of the coastal areas, an extraordinarily high concentration of Li was found.     

Direct determination of barium in Sea water by inductively coupled plasma emission spectrometry

A method for the determination of barium in sea water was investigated using inductively coupled plasma emission spectrometry, and sea water samples from the Japan Sea and the Pacific Ocean were directly analyzed by this method. Artificial sea water was used to prepare matrix matched standard solutions to overcome the problem of physical interference. The detection limit (signal/noise ratio=2) for barium in deionized and distilled water was 0.08µg l^?1 and in sea water, 0.12µg l^?1. The reproducibilities in the purified water and in the sea water at the 10µg l^?1 level were 0.7% a#FFFFFFnd 0.5%, respectively. The barium concentration in both the Japan Sea and the Pacific Ocean increased with depth and ranged between 5.5–10.0µg l^?1 and 4.1–18.4µg l^?1, respectively.     

On a time-symmetric Hermite integrator for planetary N-body simulation

We describe a P(EC) ⁿ Hermite scheme for planetary N -body simulation. The fourth-order implicit Hermite scheme is a time-symmetric integrator that has no secular energy error for the integration of periodic orbits with time-symmetric time-steps. In general N -body problems, however, this advantage is of little practical significance, since it is difficult to achieve time-symmetry with individual variable time-steps. However, we can easily enjoy the benefit of the time-symmetric Hermite integrator in planetary N -body systems, where all bodies spend most of the time on nearly circular orbits. These orbits are integrated with almost constant time-steps even if we adopt the individual time-step scheme. The P(EC) ⁿ Hermite scheme and almost constant time-steps reduce the integration error greatly. For example, the energy error of the P(EC)² Hermite scheme is two orders of magnitude smaller than that of the standard PEC Hermite scheme in the case of an N  = 100,  m  = 10²⁵ g planetesimal system with the rms eccentricity 〈 e ²〉^1/2 ≲0.03.     

Similarity of electrophoretic dissolved protein spectra from coastal to pelagic seawaters

Dissolved proteins in seawater samples collected from a coastal area of Tokyo Bay, Sagami Bay and a location off the Kuroshio Current were investigated by one-dimensional sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) and high resolution two-dimensional electrophoresis (2-DE). Four to nine protein bands were detected in SDS-PAGE in the apparent molecular weight (MW) range from 12 kilo Dalton (kDa) to 49 kDa. The 2-DE technique distinguished 10 to 46 protein spots exhibiting isoelectric point (pI)/MW ranging 4.3–9.2/12–63 kDa. The elecrophoretic patterns were similar between the coastal and pelagic samples, as well as previously reported patterns from various pelagic areas. The close similarity of electrophoretic mobility on both SDS-PAGE and 2-DE gels indicates the compositional homogeneity of dissolved proteins in seawater throughout a broad range of marine environments. Proteinaceous dissolved organic matter (DOM) that was unresolved and smeared staining characteristics on both SDS-PAGE and 2-DE gels was first observed in Tokyo Bay waters in the present study and its possible sources are discussed. Although the two protein species, 48 kDa and 39 kDa proteins, have been identified as homologues of Porin P and low molecular weight-alkaline phosphatase of Pseudomonas aeruginosa PAO1, respectively, four strains of P. aeruginosa and two species of Pseudomonas spp. have been newly identified as the source organisms of these proteins using the N-terminal amino acid sequence data determined in previous studies.     

Possible change in distribution of seaweed, Sargassum horneri, in northeast Asia under A2 scenario of global warming and consequent effect on some fish

Global warming effects on seaweed beds are already perceptible. Their geographical distributions greatly depend on water temperatures. To predict future geographical distributions of brown alga, Sargassum horneri, forming large beds in the northwestern Pacific, we referred to future monthly surface water temperatures at about 1.1° of longitude and 0.6° of latitude in February and August in 2050 and 2100 simulated by 12 organizations under an A2 scenario of global warming. The southern limit of S. horneri distribution is expected to keep moving northward such that it may broadly disappear from Honshu Island, the Chinese coast, and Korean Peninsula in 2100, when tropical Sargassum species such as Sargassum tenuifolium may not completely replace S. horneri. Thus, their forests in 2100 do not substitute those of S. horneri in 2000. Fishes using the beds and seaweed rafts consisting of S. horneri in East China Sea suffer these disappearances.     

The inventory and chemical characterization of dissolved proteins in oceanic waters

One-dimensional sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) and high resolution two-dimensional electrophoresis (2-DE) were applied to separate protein molecules in dissolved organic matter (DOM) from oceanic waters. Results were: (1) The 2-DE distinguished a total of 412 protein spots in 10 samples from five water columns over the Pacific, although fewer than 30 proteins were resolved as bands from the identical samples by SDS-PAGE. (2) Major and ubiquitous protein bands (34 and 39 kDa proteins) on the SDS-PAGE gel were resolved into horizontally spread arrays (trains) of spots on the 2-DE gels, indicating that these bands were a mixture of protein species that have the same molecular weight (MW) but different isoelectric points (pIs). (3) Proteins that exhibited such electrophoretic patterns on the 2-DE gels were glycosylated with variable linkages between the sugar and polypeptide chains. (4) N-terminal amino-acid sequencing demonstrated that individual spots within each train of spots had identical N-terminal amino-acid sequences.The N-terminal amino-acid sequences of the 39 and 34 kDa glycoprotein spots in samples collected at different sites were also identical. Protein isoforms with the same amino-acid sequence but different glycosylation profiles, termed glycoforms, were often observed on the 2-DE gel. Thirty-one and 24 spots on the 2-DE gels were glycoforms of two glycoproteins with MWs of 39 and 34 kDa, respectively; they were one protein species. The glycoforms of the 39 kDa protein were identified as a low molecular weight alkaline phosphatase (L-AP) of Pseudomonas aeruginosa PAO1 by a homology search through five amino-acid sequence databases. The present and earlier work indicates that all identified source organisms of dissolved proteins belong to the Pseudomonas group. We propose the hypothesis that proteins associated with membrane vesicles liberated from a minor member of the bacterioplankton assemblage, the marine Pseudomonas group, are one of the important sources of dissolved proteins in oceanic waters. This hypothesis may apply to the source pathway and survival not only of proteins and also to the universally occurring bacterial peptidoglycan and lipopolysaccharide components in DOM.     

Vertical transport of organic materials in the northern North Pacific as determined by sediment trap experiment

Sediment traps were deployed at 5 depths of 100 through 5,250 m to collect suspended sediments in the northern North Pacific (47°51.1'N; 176°20.6'E, 5,300 m deep) in the summer of 1978. Fatty acid composition was determined in the samples of phytoplankton, particulate matter, trap sediment and bottom sediment.Fatty acid composition of the trap sediments revealed no significant vertical trend throughout the water column from depths of 100 to 5,250 m, and were also similar to those of the phytoplankton and the particulate matter from the euphotic layer. However, a marked difference in the fatty acid composition was observed between the trap sediments and the particulate matter from deep waters. Therefore, it can be concluded that the source of fatty acids in the trap sediments is the particulate matter from the euphotic layer but not from deep waters.Unsaturated fatty acids highly susceptible to biological agents were rather abundant in the trap sediments as well as in the phytoplankton and particulate matter from the euphotic layer, however no unsaturated fatty acid was found in the particulate matter from deep waters. From these findings, it is clear that the particulate matter of the euphotic layer is transported to deep waters very rapidly. As the sinking rate of fecal pellets produced by zooplankton is in the range of ten to hundreds of meters a day, fecal pellets are assumed to be the most likely carrier of rapid-transport of organic matter including fatty acids from the euphotic layer to deep waters.     

Detection of Vibrio (Listonella) Anguillarum Porin Homologue Proteins and Their Source Bacteria from Coastal Seawater

The molecular distribution of dissolved proteins in seawater from coastal marine environments in Uranouchi Bay, Kochi Prefecture, is first reported in this article. Occurrence of bacteria-derived dissolved proteins and their source bacteria were examined using a probe of the antibody (anti-Omp35La) against a porin outer membrane protein (Omp35La) of the fish pathogenic bacterium Vibrio (Listonella) anguillarum. The electrophoretograms of dissolved proteins from coastal seawater showed a large number of discrete and individual proteins overlapped each other over a wide range of molecular masses indicating active processes in coastal environments in transferring proteins from organisms to the inanimate dissolved protein pool. Among the dissolved proteins, 37 kDa- and 18 kDa-proteins reacted with the Omp35La. In order to isolate the source bacteria of such dissolved proteins, bacteria from seawater and diseased fish were screened by colony Western blotting with anti-Omp35La. The reactive strains were further examined in sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE)/Western blotting to verify the presence of Omp35La homologues among the outer membrane proteins of such strains. Outer membrane proteins reacting with anti-Omp35La were detected in only 4 strains of the 129 strains that were positive in the colony Western blotting. The level of possible source bacteria of 37 kDa- and 18 kDa-dissolved proteins was suggested to be 5–6 orders of magnitude lower than the total bacterial count. The present study leads us to hypothesize that a minor portion of the bacterial assemblage is responsible for the dissolved proteins in the coastal waters.