Marine environmental studies on outbreaks of red tides in neritic waters

The cause of red tides appearing in neritic waters in Japan have been discussed by several workers in relation to the development of eutrophication. The author has been engaged in marine environmental studies on outbreaks of red tides, mainly, in the Seto Inland Sea since 1964 using a combination of the following approaches:

1. surveys of the red tides that have occurred,
2. elucidation of the oceanographical and biological characters of the water areas where red tides occur,
3. isolation of the red tide organisms for physiological studies of their growth,
4. chemical and biological assays of the growth promoting factors, and
5. estimation of the effects of pollutants on the growth of the red tide organisms.

The red tide organisms surveyed wereEutreptiella sp. (Euglenophyceae),Dictyocha fibura (Chrysophyceae),Chattonella marina, C. antiqua, Fibrocapsa japonica, Heterosigma akashiwo (Chloromonadophyceae),Prorocentrum minimum, P. triestinum, Gymnodinium mikimotoi, G. nelsoni, Gymnodinium type '65,Noctiluca miliaris, Protogonyaulax catenella, Gonyaulax polygramma, Peridinium quinquecorne (Dinophyceae) andMesodinium rubrum (Ciliata). Most of these species were isolated and cultured for physiological studies. Algal growth potential in sea water was assayed in Hiuchi Nada and Beppu Bay. Growth promoting activity was found in sea water about 2km off shore from the industrial zone which locates along the coast of Beppu Bay. The effects of industrial wastes were examined forEutreptiella sp.,Heterosigma akashiwo andProrocentrum triestinum. Sulfite pulp waste caused marked promotion of growth in these organisms. The growth promoting activity of the waste was elucidated by chelation of the waste with iron. After the oil spill which occurred at Mizushima Bay in 1974, a heavy red tide ofNoctiluca miliaris appeared, followed byProrocentrum minimum. Polycyclic and polar fractions in heavy oil separated by chromatography were suspected to be the growth promoting substances. Natural growth promoting chemicals, uracil and thymine, were found in interstitial water of bottom mud of Beppu Bay in concentrations of 58–120, and 28–83?g per 100 g dry mud, respectively. The mechanism of fish kills caused by red tides was another subject of study.     

Allelopathic growth inhibition of Heterosigma akashiwo by the three Ulva spcieces (Ulva Pertusa, Ulva Linza, Enteromorpha intestinalis) under laboratory conditions

Allelopathic effects of several concentrations of fresh tissue,dry powder and dry tissue of three bloom-forming green macroalgae Ulva pertusa,Ulva linza and Enteromopha intestinalis on the red tide microalga Heterosigma akashiwo were evaluated in microcosms systems.The effects of macroalgae culture medium filtrate were investigated on H.akashiwo using initial or semi-continuous filtrate addition.Preliminary studies on the algicidal effects of one aqueous and four organic solvent extracts from the macroalgae on the microalga were carried out to confirm the existence of allelochemicals in the tissue of these macroalgae.The dry powder of U.pertusa was extracted with methanol,and the methanol extracts were partitioned to petroleum ether phase,ethyl acetate phase,butanol phase and distilled phase by liquid-liquid fractionation.The bioassays of the activity of every fraction were carried out on H.akashiwo.The resultant microcosms assay showed that the growth of H.akashiwo was strongly inhibited by using fresh tissues,dry powder or dry tissue of these three macroalgae,while aqueous and methanol extracts of both macroalgae had strong inhibitory effects on the growth of H.akashiwo,and the EC 50 values for methanol extract of U.pertusa,U.linza or E.intestinalis were 0.016,0.028×10-12 or 0.033×10-12,respectively.While the other three organic solvent extracts（acetone,ether and chloroform） had no apparent effect on its growth,this suggests that the allelochemicals from these three macroalgae had relatively high polarities.The activity of petroleum ether phase,ethyl acetate phase,butanol phase and distilled phase of U.pertusa methanol extract was carried out on H.akashiwo indicating that petroleum ether phase and ethyl acetate phase had stronger algicidal effect on H.akashiwo.The inhibition effect of the ethyl acetate phase was not as strong as that of petroleum ether phase,and effective concentration of petroleum ether phase was 17 mg/L for H.akashiwo.However,no significant algicidal effects were observed on the butanol phase and distilled water phase.These three macroalgae＇s culture medium filtrate exhibited no apparent growth inhibitory effect on the microalga under initial filtrate addition whereas the growth of H.akashiwo was significantly inhibited under semi-continuous filtrate addition,which suggests that continuous release of small quantities of rapidly degradable allelochemicals from the fresh tissue of both macroalgae was effective in inhibiting the growth of H.akashiwo.     

Effects of temperature on the vegetative cell liberation of seven species of red-tide algae from the bottom mud in Osaka Bay

Mud samples were collected from the eastern coast of Osaka Bay from April 1984 to August 1985 and were incubated atin situ mud temperatures to examine the effects of temperature on the liberation of seven species of red-tide algae. Skeletonema costatum appeared extensively over a wide temperature range of 9–25°C. The percentage of liberation of benthicHeterosigma akashiwo cells tended to decrease with decreasing temperature, but this species also showed high percentages of liberation (40–100 %) in April whenin situ mud temperatures were still low (9.5–10°C). Germination of benthicHeterocapsa triquetra cells was active at temperatures lower than 10°C but was inhibited to below 20% at temperatures higher than 21°C. This indicates that the supply of vegetativeHeterocapsa cells from bottom muds to seawaters becomes inactive from summer to early autumn. The optimum temperature range for the liberation of benthicChattonella sp. cells was 16–21°C. ForProrocentrum micans, Prorocentrum minimum, andProrocentrum triestinum, no vegetative cells were released from bottom mud at any of the temperatures examined (9–25°C).Field observations on the population dynamics of vegetative cells conducted from April to September 1984 revealed that a close link exists between liberation ofS. costatum andH. triquetra and their blooms in the waters of Osaka Bay. On the basis of these findings, the ecological role of benthic cells in initiating red tides in Osaka Bay is discussed.     

Change in the microzooplankton community during decay of aHeterosigma akashiwo bloom

The temporal change in the microzooplankton community during the decay of a bloom ofHeterosigma akashiwo was investigated over a 10-day period in June–July 1991 at a site in western Hiroshima Bay, the Seto Inland Sea, Japan. The density ofH. akashiwo was at the order of 10⁴ cells·ml^–1 during the first 5 days, and decreased drastically when vertical mixing occurred.Heterosigma akashiwo cells disappeared after the eighth day. When the density ofH. akashiwo decreased suddenly, the density of microzooplankton increased rapidly. The increase in microzooplankton density was due to non-tintinnid ciliates. The species diversity of tintinnids was significantly higher in 1 and 2-m layers during the post-bloom period than during the bloom period. One species of tintinnid,Codonellopsis nipponica, was the most abundant in the bottom layer during the bloom period but decreased in abundance during the decay of the bloom. Populations of two species of hyaline tintinnids,Eutintinnus tubulosus andHelicostomella longa, were at low levels during the bloom period, and then developed suddenly after the bloom disappeared. It was demonstrated that the abundance and species composition of the ciliate community change dramatically during the decay of theHeterosigma bloom.     

海州湾赤潮高发区浮游细菌与赤潮及环境因子的关系

海州湾是南黄海赤潮高发区之一。为研究浮游细菌与赤潮及环境因子的关系,于2020年11月在海州湾赤潮期间进行了现场调查,采集了8个站位的浮游细菌、浮游植物样品,获取了温度、盐度、叶绿素a以及氮、磷、硅营养盐浓度等环境因子信息,分析了赤潮原因种及浮游细菌群落结构情况。结果显示,此次赤潮原因种为三叶原甲藻(Prorocentrum triestinum)、赤潮异弯藻(Heterosigma akashiwo)及塔胞藻(Pyramimonas sp.),发生赤潮时水温、盐度较低,盐度与赤潮异弯藻的分布有一定的联系。使用16SrRNA高通量测序方法分析调查海域的浮游细菌情况,结果显示赤潮发生站位的浮游细菌多样性略低于其他非赤潮发生站位,优势细菌与其他站位有明显不同,以假单胞菌目(Pseudomonadales)、红杆菌目(Rhodobacterales)和黄杆菌目(Flavobacteriales)为主。赤潮发生站位的浮游细菌群落结构也存在一定的差异,不同站位可能处于不同的赤潮阶段,对浮游细菌群落具有不同的影响。相关性分析显示,黄杆菌目与叶绿素a显著正相关,表明黄杆菌目与赤潮发生有一定的关系。     

粘土-MMH体系絮凝赤潮生物的动力学研究

根据分子碰撞理论和粘土表面改性对絮凝作用的影响,进行了粘土－ＭＭＨ体系絮凝沉降赤潮异弯藻（Ｈｅｔｅｒｏｓｉｇｍａ ａｋａｓｈｉｗｏ针藻）和新月菱形藻（Ｎｉｔｚｓｃｈｉａ ｃｌｏｔｅｒｉｕｍ）硅藻）表面电性,并对上述两种藻进行絮凝动力学实验。结果表明,一定颗粒度的粘土对赤潮异弯藻和新月菱表藻的絮凝速率随体系中ＭＭＨ比例的增大而呈不同程度的提高,对于粘土／ＭＭＨ比一定的混合体系,絮凝速率随粘土浓度的增     

铁、氮、磷、维生素B1和B12对海洋原甲藻的生长效应

４因子，２水平（铁为４水平）正交试验表明：络合铁和硝态氮对海洋原甲藻的生长有极显著的促进作用（Ｐ＜０．０１），维生不Ｂ１，Ｂ１２混合液有显著促进作用（Ｐ＜０．０５）。络合铁和硝态氮为大鹏湾浮游植物生长的营养限制因了。而磷酸盐的作用不显著。     

赤潮异弯藻有色可溶性有机物的变化以及对其他微藻的影响

赤潮消长显著影响海洋中有色可溶性有机物(CDOM)的变化.赤潮异弯藻(Heterosigma akashiwo)是一种常发的鱼毒性赤潮种类,是产生CDOM较显著的种类.本文以赤潮异弯藻CDOM为研究对象,分析了CDOM在种群消长中的变化特征,研究了光对赤潮异弯藻CDOM组成物质变化的影响,并就此变化对其他微藻种群生长造成的影响进行了定量研究.结果表明:(1)以紫外吸收的定量变化为指标,赤潮异弯藻CDOM的量与种群消长呈互逆相关:种群密度增加, CDOM降低;种群密度降低, CDOM增加;长期培养种群中, CDOM含量增加.(2)光对该藻产生的CDOM物质组成和定量有显著影响,紫外照射能显著漂白CDOM,类腐殖质和腐殖酸降解明显.(3)该藻CDOM变化影响其他微藻种群生长:CDOM显著促进微小卡罗藻(Karlodinium micrum)、小硅藻(Nitzschia closterium f. minutissima)的种群生长,受光降解后对小硅藻的促进作用降低,但对微小卡罗藻的促进作用不变; CDOM 抑制海洋原甲藻(Prorocenturm micans)种群生长,光降解后,其抑制作用降低.赤潮异弯藻赤潮产生的大量且稳定的CDOM可以影响海洋微型生物群落结构.     

Benzo(a)pyrene in the sediment of Osaka Bay and Keihin Canal and its estimated sources

Benzo(a)pyrene (BP) in the sediment of Osaka Bay were determined. High concentration was found at two stations near the mouth of Shin-Yodo and off Kobe respectively (0.98g g^–1 dry mud basis, 1.1g g^–1). The concentration decreases regularly from the mouth of the river further into the bay. The other supplemental determination was carried on the sediment and the seawater of Keihin Canal. Notable BP concentration of 89g g^–1 was observed in the sediment beneath the effluent outlet of a gasworks. The BP in the sediment near the ironworks was also considerable, while the BP was relatively less in the sediment beneath the effluent outlet of refineries. These data suggest that coke plants working in gasworks or ironworks may be the larger sources of BP than refineries. The results of Osaka Bay coincide with this hypothesis.Cadmium, lead, copper, zinc, nickel, ignition loss and fine sand content were measured from the same sediment samples of Osaka Bay. Cd, Pb, Cu and ignition loss showed the regular distributions which resemble to BP and accordingly, good correlations with BP. No significant correlations were found between BP and Ni, Zn and fine sand content which showed no regular distributions.     

Chemical environment for red tides due toChattonella antiqua

In order to assess the roles of Fe and Cu in outbreaks ofChattonella antiqua red tide, concentrations of these metals in the surface seawater were monitored around the Ie-shima Islands in the Seto Inland Sea during the summers of 1986–1988. Bioassay of the surface seawater with respect to Fe and Cu was also conducted using a cultured strain ofC. antiqua.Concentrations of Fe and Cu in the filtered seawater (Fe^F and Cu^F) were in the range of 3.9–10.0 and 9.3–11.2 nM, respectively. The bioassay with respect to Fe revealed that Fe at the surface layer was usually insufficient to support the maximum growth rate ofC. antiqua, except whenC. antiqua was dominant in the field. However, correlations between Fe^F and the growth rate of the control cultures (Fe, EDTA=not enriched; N, P, B₁₂=enriched at optimum levels) were not apparent, probably because Fe^F did not reflect the concentration of available Fe.The bioassay with respect to Cu was coupled with the Cu^F values obtained. The results indicated that Cu at the surface layer was detoxified by complexation with natural organic ligand(s), and that pCu (=minus log of cupric ion activity) was 11.5–11.7, optimum for the growth ofC. antiqua, throughout the survey period. It is suggested that Fe, but not Cu, is a potentially important factor in regulating the natural populations ofC. antiqua in the Seto Inland Sea.     

Chemical environment for red tides due toChattonella antiqua in the seto inland sea,Japan

Severe red tides due toChattonella antiqua occur sporadically during summer in the Seto Inland Sea, Japan, and cause significant damage to the fishing industry. In order to assess the chemical environment with respect to the outbreak ofC. antiqua, environmental factors that affect the growth ofC. antiqua were monitored around the Ie-shima Islands, the Seto Inland Sea, in the summer of 1986. In addition, a growth bioassay of the seawater usingC. antiqua was conducted under a semicontinuous culture system. Although temperature, salinity and light intensity were optimum for the growth ofC. antiqua, red tides by this species did not occur. Concentrations of NH ₄ ⁺ , NO ₃ ^? and PO ₄ ^3? were low (<0.4, <0.2, <0.06 µM, respectively) above the thermocline (8–12 m) and high below it (0.6–2, 4–8, 0.4–0.8 µM, respectively). Vitamin B₁₂ concentrations did not change significantly between the surface (0 m) and below the thermocline (25 m) in the level of 2–4 ng·l^?1. The growth bioassay revealed that in the surface waters, concentrations of N- as well as P- nutrients were too low to support a rapid growth ofC. antiqua. At the depth of 25 m, neither N, P nor B₁₂ limited the growth rate. In order to obtain more quantitative information on the growth rate as a function of the concentrations of N- and P- nutrients,C. antiqua was grown in a semicontinuous culture system by changing nutrient concentrations systematically. The observed growth rate (μ) can be approximated as follows: $$\mu = \mu _{\max } .\frac{{S_N }}{{K_g ^N + S_N }}.\frac{{S_{PO4} }}{{K_g ^P + S_{PO4} }},$$ whereS _N is the concentration of NO ₃ ^? plus NH ₄ ⁺ (0–6 µM),S _PO, the concentration of PO ₄ ^3? (0–0.6 µM), μ_max (0.97 d^?1) the maximal growth rate,K ₀ ^N (1.0 µM) andK ₀ ^P (0.11 µM) the half saturation constants for NO ₃ ^? and PO ₄ ^3? , respectively. Using the above equation with nutrient concentrations measured, the rate at which seawater supports the growth ofC. antiqua can be estimated and this can be used for the assessment of chemical environments with respect to the outbreak ofC. antiqua.     

Simultaneous Measurement of Hydrogen Peroxide and Fe Species (Fe(II) and Fe<Subscript>(tot)</Subscript>) in Okinawa Island Seawater: Impacts of Red Soil Pollution

The northern part of Okinawa Island suffers from red soil pollution—runoff of red soil into coastal seawater—which damages coastal ecosystems and scenery. To elucidate the impacts of red soil pollution on the oxidizing power of seawater, hydrogen peroxide (HOOH) and iron species including Fe(II) and total iron (Fe_(tot), defined as the sum of Fe(II) and Fe(III)) were measured simultaneously in seawater from Taira Bay (red-soil-polluted sea) and Sesoko Island (unpolluted sea), off the northern part of Okinawa Island, Japan. We performed simultaneous measurements of HOOH and Fe(II) because the reaction between HOOH and Fe(II) forms hydroxyl radical (•OH), the most potent environmental oxidant. Gas-phase HOOH concentrations were also measured to better understand the sources of HOOH in seawater. Both HOOH and Fe(II) in seawater showed a clear diurnal variation, i.e. higher in the daytime and lower at night, while Fe_(tot) concentrations were relatively constant throughout the sampling period. Fe(II) and Fe_(tot) concentrations were approximately 58% and 19% higher in red-soil-polluted seawater than in unpolluted seawater. Gas-phase HOOH and seawater HOOH concentrations were comparable at both sampling sites, ranging from 1.4 to 5.4 ppbv in air and 30 to 160 nM in seawater. Since Fe(II) concentrations were higher in red-soil-polluted seawater while concentrations of HOOH were similar, •OH would form faster in red-soil-polluted seawater than in unpolluted seawater. Since the major scavenger of •OH, Br⁻, is expected to have similar concentrations at both sites, red-soil-polluted seawater is expected to have higher steady-state •OH concentrations.     

A tidal front in winter influenced by river discharge

Water quality of Osaka Bay is greatly influenced by freshwater discharge from rivers, to the effect of salinity playing a major role in forming the stratification. The tidal front is expected to appear in such an area even in winter considering the theory of the formation of a tidal front. From the field observation, we recognized a tidal front in winter for the first time in Osaka Bay. The critical value of a parameter log(H/U ³) for generation of a tidal front is obtained as a function of river discharge and cooling effect through sea surface. Differences of nutrients (NH₄–N, PO₄–P) concentration across the front are not clear, probably because they are utilized by phytoplankton easily. But in (NO₂–N)+(NO₃–N), DIN, PP and T–P, there is a discontinuity structure across the front, even if the absolute value of concentration difference is small.     

Vertical distributions of nitrogen,phosphorus and iron in Beppu Bay

Beppu Bay is a shallow basin located at the western end of the Seto Inland Sea with a sill depth ofca. 40 m. The bottom water (belowca. 65 m in summer andca. 70 m in winter) was anoxic and contained high concentrations of hydrogen sulfide, phosphate and ammonium. Maximum concentrations of nitrate and nitrite appeared near the top of the thermocline, suggesting the occurrence of bacterial nitrification in this layer and of bacterial denitrification in the anoxic bottom water. Concentrations of particulate phosphorus and particulate iron were highest near the bottom of the thermocline. The distribution of phosphorus in this bay is probably controlled by a dissolution-diffusion-precipitation cycle of iron or its hydrous oxides.     

The influence of increased iron concentration on survival and growth of seedlings and young plants of eelgrass Zostera marina

Iron (Fe) is an essential nutrient for plants but toxic at high concentrations. We subjected seedlings and young plants of eelgrass Zostera marina to different seawater iron concentrations (500, 600, 700, 800, 1,000 and 1,500 μg/L) for 30 days under controlled laboratory conditions. Natural seawater without added iron (500 μg/L) was used as reference seawater. No sediments were provided to avoid iron scavenging by particle surfaces in the sediment. We measured plant response in terms of survivorship, morphology, growth rate and productivity. Survival analysis combined with morphological, dynamic and productive assessment suggested that the optimum seawater iron concentration for the establishment of Z. marina seedlings and young plants is 700 μg/L. The no observed effect concentration, lowest observed effect concentration, lethal concentration that caused an increase in mortality to 10% of that of the control, and the effect concentration that caused a decrease in growth to 10% of that of the control values of young plants were significantly lower than those of seedlings, implying an increased sensitivity to high Fe concentrations (>1,000 μg/L). This study further develops our understanding of the physiological ecology of the early life stages of Z. marina and provides data that could prove helpful in the development of successful eelgrass restoration and conservation.     

Cell contact-dependent lethal effect of the dinoflagellate Heterocapsa circularisquama on phytoplankton–phytoplankton interactions

We used bi-algal culture experiments to investigate and verify the roles of growth interaction between Heterocapsa circularisquama and Prorocentrum dentatum in monospecific bloom formation. Growth of H. circularisquama was slightly inhibited when inoculated at 10² cells mL^–1 along with P. dentatum at 10⁴ cells mL^–1. In other combinations of inoculation densities, P. dentatum density rapidly decreased to extremely low levels in the presence of H. circularisquama. We used a mathematical model to simulate growth and interactions of H. circularisquama and P. dentatum in bi-algal cultures. The model indicates that one species will always inhibit the growth of the other and that the relative initial cell densities of the species are critical in determining the outcome. When cultured together under conditions without cell contact, growth of H. circularisquama and P. dentatum was not inhibited. As with P. dentatum, the growth of Heterosigma akashiwo and Skeletonema costatum was inhibited in intact cell suspensions with H. circularisquama, but a nontoxic species, Heterocapsa triquetra, did not affect the growth of P. dentatum or the other species. Similarly, cell suspensions of H. circularisquama showed hemolytic activity toward rabbit erythrocytes, but those of H. triquetra did not. In addition, the cell-free supernatant of H. circularisquama cultures showed no significant hemolytic activity. These results suggest that H. circularisquama causes lethality in P. dentatum by direct cell contact in which live-cell-mediated hemolytic activity might be a contributing factor.     

Changes of seawater quality in Ofunto Bay,Iwate, after the 2011 off the Pacific coast of Tohoku Earthquake

Ofunato Bay was a semi-closed area because of the breakwater effect at the entrance; however, the breakwater was destroyed by a massive tsunami generated by the 2011 off the Pacific coast of Tohoku Earthquake. Consequently, the physical environment of Ofunato Bay has been changed significantly, i.e., the modification of the stratified structure of seawater inside the bay and the intermittent intrusion of seawater outside the bay. These alterations of physical environment are considered to have an influence on the chemical and biological environment in Ofunato Bay. To elucidate the influence of the tsunami on the aquatic environment, we measured dissolved nutrients, chlorophyll a and dissolved oxygen concentrations, and heterotrophic bacteria abundance inside and outside of Ofunato Bay from 2012 to 2014, and compared these data with those obtained before the earthquake. As compared with before the earthquake, significant changes after the earthquake were (1) decrease of ammonium and phosphate concentrations, (2) increase of chlorophyll a concentration, (3) increase of dissolved oxygen concentration in the bottom, and (4) decrease of heterotrophic bacteria abundance. The collapse of the breakwater and consequential enhanced water exchange were considered to have brought the decrease of nutrient concentration inside the bay. Furthermore, washout of shellfish mariculture rafts by the tsunami decreased the shellfish biodeposits along with the elution of nutrients by heterotrophic bacteria. Decrease of cultivated shellfish further caused a decline in feeding pressure on phytoplankton and, subsequently, increased the phytoplankton biomass that contributed to the decrease of nutrients inside the bay.     

Characteristics and regional classification of the copepod community in Ariake Bay with note on comparison with 3 decades ago

Ariake Bay, Kyushu Island, has recently exhibited environmental degradation in the form of red tides and anoxic bottom water. To determine the characteristics and regional classification of the copepod community, zooplankton surveys were made throughout the bay in three cruises each in October 2004, January 2005 and March 2009 by vertical tows of a 0.1-mm-mesh plankton net. Oithona davisae was the most abundant in January and March, and Microsetella norvegica in October. Cluster analysis revealed that the copepod community from each cruise was generally separated into the inner to eastern-middle region and the western-middle to mouth region. A SIMPER analysis revealed that dissimilarity between the groups and similarity within each group were mainly due to the dominant species, but the similarities within the outer-region group in January and March were mostly contributed by Paracalanus parvus s.l. A non-metric multidimensional scaling with bubble plots of environmental variables and a BIOENV analysis showed that transparency was more different between the two groups than temperature and salinity. As compared with two similarly sized, eutrophic bays (Tokyo and Osaka Bays), Ariake Bay differs from Tokyo Bay in the dominance of M. norvegica and from Osaka Bay in the high abundance of O. davisae even in the colder season. The dominant species and the regional classification of the copepod community in the bay were similar to those in the studies in the 1970s, suggesting that the copepod community has not notably changed during the last 3 decades.     

Investigations of iron coordination and redox reactions in seawater using Fe radiometry and ion-pair solvent extraction of amphiphilic iron complexes

Iron coordination and redox reactions in synthetic and coastal seawater were investigated at nanomolar concentrations using ⁵⁹Fe radiometry and ion-pair solvent extraction of iron chelated by sulfoxine (8-hydroxyquinoline-5-sulfonate) and BPDS (bathophenanthroline disulfonate). Using sulfoxine, we determined the rate at which the monomeric Fe(III) hydroxide species present in seawater of pH 8 are complexed by the microbial siderophore deferriferrioxamine B and the synthetic chelator EDTA (ethylenediaminetetraacetic acid). Forward rate constants of 2 × 10⁶M⁻¹s⁻¹ and 20 M⁻¹s⁻¹, respectively, were obtained. The kinetics of these reactions have not been measured previously at pH values near that of seawater. Conditional equilibrium constants measured for the Fe(III)-EDTA system are consistent with published stability constants for EDTA complexes and for Fe(III) hydrolytic equilibria minus the neutral Fe(OH)₃^o species, suggesting it is not quantitatively significant near pH 8. Commercial humic acid was found to have sufficient affinity for iron to compete with Fe(III) hydrolysis in seawater, and limited evidence was obtained for an interaction with dissolved organic matter in coastal seawater.In our investigations of redox reactions using BPDS to trap Fe(II) produced in the medium, we observed enhanced photoreduction of Fe(III) by humic acid as well as reduction induced by solutes released from phytoplankton in seawater of pH 8. Although the method is sensitive enough to work at near-oceanic levels of iron, the difficulty in distinguishing Fe(II) generated by Fe(III)-BPDS interactions from Fe(II) produced by other means limits its utility. This analytical ambiguity may be generalizable to other methods which measure ferrous iron in seawater using Fe(II)-specific ligands.     

Life habit of vesicomyid clam,Calyptogena soyoae,and hydrogen sulfide concentration in interstitial waters in Sagami Bay,Japan

In and around the beds of vesicomyid clam (Calytogena soyoae) located off Hatsushima Island in Sagami Bay, central Japan, hydrogen sulfide concentration in bottom water and interstitial water was measured every 10 cm from just above seafloor to 40 cm deep usingin situ separative dialysis bags. While hydrogen sulfide over 0.01 mmol/kg was not measured from the seawater just above the dense clam beds, the concentration of hydrogen sulfide increased rapidly below 10 cm deep. The results indicate that the habit of the clam is correlated with high concentration of hydrogen sulfide contained in pore waters of sediments between depths of 10 and 20 cm from the bottom surface. Concentrations of hydrogen sulfide ranging from approximately 0.05 mmol/kg to 0.6 mmol/kg might be suitable requirement for the habitat ofC. soyoae.