Adsorption of tributyltin by tributyltin resistant marine Pseudoalteromonas sp. cells

The isolate, Pesudoalteromonas sp. TBT1, could grow to overcome the toxicity of tributyltin chloride (TBTCl) up to 30 μM in the absence of Cl⁻ in the medium until the cells reached an exponential phase of growth. The viability, however, was reduced after the cells reached a stationary phase. The degradation products, such as dibutyltin (DBT) and monobutyltin (MBT), were not detected in the growth medium, indicating that the isolate has no ability to degrade TBT into less toxic DBT and MBT. Up to about 10^7.5 TBT molecules were adsorbed by a single cell. The observation of morphological changes with an electron microscope showed that the cell surface became wrinkled after exposure to the lethal concentration of 10 mM TBTCl. These results indicate that the resistance of the isolate toward the toxicity of TBTCl is not related to the unique cell surface, which seems to play an important role in preventing the diffusion of TBTCl into the cytoplasm.     

Adsorption of tributyltin by tributyltin resistant marine Pseudoalteromonas sp. cells

The isolate, Pesudoalteromonas sp. TBT1, could grow to overcome the toxicity of tributyltin chloride (TBTCl) up to 30 microM in the absence of Cl(-) in the medium until the cells reached an exponential phase of growth. The viability, however, was reduced after the cells reached a stationary phase. The degradation products, such as dibutyltin (DBT) and monobutyltin (MBT), were not detected in the growth medium, indicating that the isolate has no ability to degrade TBT into less toxic DBT and MBT. Up to about 10(7.5) TBT molecules were adsorbed by a single cell. The observation of morphological changes with an electron microscope showed that the cell surface became wrinkled after exposure to the lethal concentration of 10 mM TBTCl. These results indicate that the resistance of the isolate toward the toxicity of TBTCl is not related to the unique cell surface, which seems to play an important role in preventing the diffusion of TBTCl into the cytoplasm.     

Assessment of tributyltin contamination in a shipyard area using a mussel transplantation approach

Mussels (Mytilus galloprovincialis) were transplanted to seven stations around a large shipyard for 126 days to evaluate tributyltin (TBT) contamination. Although the application of TBT-based paints to ships is totally banned in Korea, butyltin compounds were found to accumulate in mussels following transplantation. Concentrations of TBT and total butyltins in transplanted mussels near the shipyard were in the range of 40–350 ng Sn/g and 74–530 ng Sn/g on a dry weight basis, respectively. Obviously, low TBT concentrations (6.0–53 ng Sn/g dw) were determined in mussels at four stations outside the shipyard. A negative gradient of TBT concentrations and TBT portion to total butyltin concentrations were found in both the surface water and transplanted mussels according to distance from the shipyard. In addition, TBT concentrations in surface water and transplanted mussels showed significant correlation (r² = 0.71; p < 0.001). These results indicate that the shipyard still releases fresh TBT into surrounding waters even after TBT regulation in Korea, and mussel transplantation is useful in evaluating TBT contamination in shipyard area.     

Differences in the acute toxicities of tributyltin between the Caprellidea and the Gammaridea (Crustacea: Amphipoda)

Tests for the acute toxicity of tributyltin (TBT) were conducted on amphipod crustaceans collected from Otsuchi Bay, Japan. Five species of caprellids and three species of gammarids, which belong to a closely related ecological niche, were used for the exposure experiments at seven test concentrations (0, 0.001, 0.01, 0.1, 1, 10 and 100 microg TBTCl/l) for 48 h at 20 degrees C. The 48-h LC50 values of the caprellids were 1.2-6.6 microg TBTCl/l, and these were significantly lower than those of the gammarids (17.8-23.1 microg TBTCl/l). This suggests that caprellids are more sensitive to TBT than gammarids. Furthermore, the proportions of TBT and its derivatives, dibutyltin (DBT) and monobutyltin (MBT), were measured in the amphipods collected from Otsuchi Bay. In the caprellids, TBT was the predominant compound, accounting for 72% of the total butyltin which reflected the butyltin ratio in seawater, while in the gammarids, TBT's breakdown products (DBT and MBT) predominated, accounting for 75% of the total butyltin. This difference suggests that caprellids may have lower metabolic capacity to degrade TBT than gammarids. Therefore, the difference in sensitivity to TBT among the amphipods is thought to be related to the species-specific capacity to metabolize TBT.     

Effects of tributyltin at concentrations below ambient levels in seawater on Caprella danilevskii (Crustacea: Amphipoda: Caprellidae)

Hatched juveniles of Caprella danilevskii (Crustacea: Amphipoda) were exposed to one of two concentrations of tributyltin (TBT) (1.1 and 10.7 ng TBT L⁻¹) for 49 d at 20 °C. These concentrations are near or below ambient levels in seawater. In both treatments and control, the survival rate was 100% at maturation, and >85% at the end of the experiments. Females reached maturation at 20 (median) to 21.5 d at instar VII, and repeated spawning 4–5 times during the experiment. The total number of juveniles per female decreased significantly from 39.5 in the control to 24.5 and 17.5 in 1.1 ng L⁻¹ and 10.7 ng L⁻¹ treatments, respectively. An earlier study reported that as the TBT concentration in seawater increased from a 0–10 ng L⁻¹ regime to a 10–20 ng L⁻¹ regime, the number of stations where Caprella spp. could be collected decreased along the coast of the Seto Inland Sea, of Japan. Thus, the present study indicates the possibility that the extremely low concentration of TBT measured in Japanese waters after 2000 lead to a reduction in reproductive success of Caprella spp.     

Removal of tributyltin (TBT) by live and dead microalgal cells

The removal of tributyltin (TBT) from artificial wastewater by dead and live cells of four microalgal species, Chlorella miniata, C. sorokiniana, Scenedesmus dimorphus and S. platydiscus was investigated. Dead cells were generally more efficient in removing TBT during three days exposure. More than 90% and 85% TBT were removed by dead cells of Scenedesmus and Chlorella, respectively. Although the removal percentages of live microalgae were smaller, TBT was continuously absorbed and degraded, and TBT removal percentages similar to respective dead cells were achieved at the end of 14 days treatment. Degradation products, DBT and MBT, were recorded mainly inside the cells, and intracellular MBT concentrations were significantly higher than DBT. In terms of TBT removal, Scenedesmus cells were more effective than Chlorella, probably due to larger cell sizes and biomass. However, TBT specific uptake and degradation by Chlorella was higher than in Scenedesmus. The highest specific TBT uptake values, as well as the highest degradation, were recorded in C. miniata, a Hong Kong isolate.     

Natural antifouling compounds produced by a novel fungus Aureobasidium pullulans HN isolated from marine biofilm

A fungus, Aureobasidium pullulans, was isolated from marine biofilm and identified. A bioassay-guided fractionation procedure was developed to isolate and purify antifouling compounds from A. pullulans HN. The procedure was: fermentation broth—aeration and addition of sodium thiosulfate–graduated pH and liquid–liquid extraction—SPE purification—GC–MS analysis. Firstly, the fermentation broth was tested for its toxicity. Then it was treated with aeration and addition of sodium thiosulfate, and its toxicity was almost not changed. Lastly, antifouling compounds were extracted at different pH, the extract had high toxicity at pH 2 but almost no toxicity at pH 10, which suggested the toxicants should be fatty acids. The EC₅₀ of the extract against Skeletonema costatum was 90.9 μg ml⁻¹, and its LC₅₀ against Balanus amphitrete larvae was 22.2 μg ml⁻¹. After purified by HLB SPE column, the EC₅₀ of the extract against S. costatum was 49.4 μg ml⁻¹. The myristic and palmitic acids were found as the main toxicants by GC–MS.     

Imposex levels and concentrations of organotin compounds (TBT and its metabolites) in Nassarius nitidus from the Lagoon of Venice

Specimens of Nassarius nitidus were collected in seven stations of the Venice Lagoon to assess the levels of tributyltin (TBT) and its metabolites monobutyltin and dibutyltin in the tissues and monitor their effect on organisms, in particular the phenomenon of imposex (superimposition of male sexual characteristics on females). The following values of population indices were found: vas deferens sequence: 1.2 ± 0.7–4.0 ± 0.5; relative penis length: 6–47%. The least impacted station was situated in the northern part of the Lagoon, where females without imposex were found and Butyltin (BuTs) concentrations in the organisms (average sum of BuTs = 43 ± 14 ng Sn g⁻¹ w.) were significantly lower than in the other stations (range of average sum of BuTs: 101 ± 22–217 ± 27 ng Sn g⁻¹ d.w.). Population indices were found to be related to the TBT content in the tissues. In particular VDSI had a significant logarithmic correlation: r = 0.95, n = 8, p < 0.05.     

Sediment PAH: Contrasting levels in the Caspian Sea and Anzali Wetland

A comparative study of 23 PAH congeners in sediment of the Caspian Sea coast and Anzali Wetland was conducted in 2010. Surface sediment was analyzed using chromatography and mass spectrometry. Total PAH concentrations ranged between 212 and 9009 ng g⁻¹ dw. Spatial distribution maps revealed that PAH levels were higher in the coastal areas of the Caspian Sea where oil related activities have been common since 1800’s. Diagnostic ratios analysis indicated that PAHs largely originated from petrogenic processes. PAH toxicity level was assessed using sediment quality guidelines and toxic equivalent concentrations to determine toxic effects on marine organism. Based on these investigations, in our study areas, the probability of toxicity for benthic organisms is “low to medium”. The toxic equivalent concentrations of carcinogenic PAHs varied between 11 and 231 ng TEQ/g; higher total toxic equivalent concentrations values were found in the coastal areas of the Caspian Sea.     

Spatial–temporal changes in Andean plateau climate and elevation from stable isotopes of mammal teeth

Paleoelevation constraints from fossil leaf physiognomy and stable isotopes of sedimentary carbonate suggest that significant surface uplift of the northern Andean plateau, on the order of 2.5 ± 1 km, occurred between ～ 10.3 and 6.4 Ma. Independent spatial and temporal constraints on paleoelevation and paleoclimate of both the northern and southern plateau are important for understanding the distribution of rapid surface uplift and its relation to climate evolution across the plateau. This study focuses on teeth from modern and extinct mammal taxa (including notoungulates, pyrotheres, and litopterns) spanning ～ 29 Ma to present, collected from the Altiplano and Eastern Cordillera of Bolivia (16.2°S to 21.4°S), and lowland Brazil. Tooth enamel of large, water-dependent mammals preserves a record of surface water isotopes and the type of plants that animals ingested while their teeth were mineralizing. Previous studies have shown that the δ¹⁸O of modern precipitation and surface waters decrease systematically with increasing elevations across the central Andes. Our results from high elevation sites between 3600 and 4100 m show substantially more positive δ¹⁸O values for late Oligocene tooth samples compared to < 10 Ma tooth δ¹⁸O values. Late Oligocene teeth collected from low elevation sites in southeast Brazil show δ¹⁸O values similar (within 2‰) to contemporaneous teeth collected at high elevation in the Eastern Cordillera. This affirms that the Andean plateau was at a very low elevation during the late Oligocene. Late Oligocene teeth from the northern Eastern Cordillera also yield consistent δ¹³C values of about ? 9‰, indicating that the environment was semi-arid at that time. Latitudinal gradients in δ¹⁸O values of late Miocene to Pliocene fossil teeth are similar to modern values for large mammals, suggesting that by ～ 8 Ma in the northern Altiplano and by ～ 3.6 Ma in the southern Altiplano, both regions had reached high elevation and established a latitudinal rainfall gradient similar to modern.     

Cosmogenic 3He and 21Ne dating of biotite and hornblende

Stable cosmogenic isotopes such as ³He and ²¹Ne are useful for dating of diverse lithologies, quantifying erosion rates and ages of ancient surfaces and sediments, and for assessing complex burial histories. Although many minerals are potentially suitable targets for ³He and ²¹Ne dating, complex production systematics require calibration of each mineral–isotope pair. We present new results from a drill core in a high-elevation ignimbrite surface, which demonstrates that cosmogenic ³He and ²¹Ne can be readily measured in biotite and hornblende. ²¹Ne production rates in hornblende and biotite are similar, and are higher than that in quartz due to production from light elements such as Mg and Al. We measure ²¹Ne_hbl/²¹Ne_qtz = 1.35 ± 0.03 and ²¹Ne_bio/²¹Ne_qtz = 1.3 ± 0.02, which yield production rates of 25.6 ± 3.0 and 24.7 ± 2.9 at g^? 1 yr^? 1 relative to a ²¹Ne_qtz production rate of 19.0 ± 1.8 at g^? 1 yr^? 1. We show that nucleogenic ²¹Ne concentrations produced via the reaction ¹⁸O(α,n)²¹Ne are manageably small in this setting, and we present a new approach to deconvolve nucleogenic ²¹Ne by comparison to nucleogenic ²²Ne produced from the reaction ¹⁹F(α,n)²²Ne in F-rich phases such as biotite. Our results show that hornblende is a suitable target phase for cosmogenic ³He dating, but that ³He is lost from biotite at Earth surface temperatures. Comparison of ³He concentrations in hornblende with previously measured mineral phases such as apatite and zircon provides unambiguous evidence for ³He production via the reaction ⁶Li(n,α)³H → ³He. Due to the atypically high Li content in the hornblende (~ 160 ppm) we estimate that Li-produced ³He represents ~ 40% of total ³He production in our samples, and must be considered on a sample-specific basis if ³He dating in hornblende is to be widely implemented.     

Distributions of polychlorinated biphenyls in the Daliao River estuary of Liaodong Bay,Bohai Sea (China)

The distributions of 41 polychlorinated biphenyls (PCBs) were determined in the aqueous phase, suspended particulate matter (SPM), and sediment of the Daliao River estuary in Liaodong Bay, Bohai Sea (China). The total PCB concentrations ranged from 5.51 to 40.28 ng L⁻¹ in the surface water, from 6.78 to 66.55 ng L⁻¹ dry weight in the SPM, and from 0.83 to 7.29 ng g⁻¹ dry weight in the sediment. The PCB concentrations in water, SPM, and sediment were moderate relative to those reported for other estuary and marine systems around the world. Sedimentary PCB concentrations decreased offshore due to the active deposition of laterally transported river-borne particles. The predominance of the highly chlorinated congeners for the water, SPM, and sediment samples are an indication of either a lack of degradation or the presence of nearby or recent releases into the environment.     

Effect of prolonged hypoxia on food consumption,respiration, growth and reproduction in marine scavenging gastropod Nassarius festivus

The effects of prolonged exposure to reduced oxygen levels (3.0 and 1.5 mg O₂ l⁻¹) on marine scavenging gastropods Nassarius festivus were studied for 8 weeks. The percentages of individuals engaged in feeding and amount of food consumed were reduced as oxygen level decreased; absorption efficiency, however, did not vary significantly with oxygen level. Oxygen consumption rates and specific oxygen consumption rates were lower at reduced oxygen levels. Reproduction occurred at all oxygen levels with less egg capsules being produced at lower oxygen levels. Egg size and number of eggs per capsule, however, were not significantly affected by oxygen level. The increase in shell length was 12%, 6% and 5% at 6.0 mg O₂ l⁻¹ (normoxia), 3.0 mg O₂ l⁻¹ and 1.5 mg O₂ l⁻¹, respectively. At the end of the experiment, the amount of energy allocated to growth and reproduction decreased at reduced oxygen levels with values obtained at 3.0 mg O₂ l⁻¹ and 1.5 mg O₂ l⁻¹ being 48% and 70% lower than those at 6.0 mg O₂ l⁻¹. At all oxygen levels, most of the accumulated energy was allocated to shell growth and reproduction, and the amount allocated to somatic growth was relatively insignificant. The reduction in energy allocated to reproduction was greater than that to shell growth as the oxygen level was reduced, indicating a strategic energy allocation of marine scavengers under stressful conditions to enhance survival.     

Occurrence of polycyclic aromatic hydrocarbons (PAHs) in seawater from the Western Taiwan Strait,China

Seawater samples (including surface water and bottom water) were collected from the Western Taiwan Strait (WTS) during June 24–25, 2009; polycyclic aromatic hydrocarbons (PAHs) in dissolved phase and particulate phase were analyzed, respectively. The results showed that the total concentrations of PAHs in the dissolved phase and particulate phase were ranged from 12.3 to 58.0 ng L⁻¹, and 10.3–45.5 ng L⁻¹, which showed a low-middle contamination level in the China Seas. The spatial variability of PAHs may be related to the complicated currents of WTS, especially the Min-Zhe coastal current. PAHs diagnostic ratios suggested that PAHs mainly originated from the inputs of pyrolytic (combustion) sources, which might be contributed to land-based atmospheric deposition. The particle-water partition coefficients of individual PAH showed that partitions were not correlated with suspended particulate matter content, dissolved organic carbon or salinity, similar to the Yangtze coastal area.     

An evaluation of the toxicity and bioaccumulation of thallium in the coastal marine environment using the macroalga,Ulva lactuca

Thallium(I) has been added to cultures of the marine macroalga, Ulva lactuca, for a period of 48 h and the accumulation of the metal and its effects on the photochemical efficiency of photosystem II (PS II) measured. Thallium elicited a measurable toxic response above concentrations of 10 μg L⁻¹ in both coastal seawater (salinity 33) and estuarine water (salinity 20). The accumulation of Tl was defined by a linear relationship with aqueous Tl and accumulation factors of about 900 mL g⁻¹ in both media. Thallium accumulated by U. lactuca that was resistant to an EDTA extraction and, by operational definition, internalised, exceeded 90% in both cases. Accumulation and toxicity of Tl in the presence of a ∼10⁵-fold excess of its biogeochemical analogue, potassium, suggests that Tl has a high intrinsic phytotoxicity and that its mode of action involves permeation of the cell membrane as Tl⁺ through NaCl–KCl co-transporter sites rather than (or in addition to) transport through K⁺ ion channels.     

Assessment of TBT and organic booster biocide contamination in seawater from coastal areas of South Korea

Seawater samples from major enclosed bays, fishing ports, and harbors of Korea were analyzed to determine levels of tributyltin (TBT) and booster biocides, which are antifouling agents used as alternatives to TBT. TBT levels were in the range of not detected (nd) to 23.9 ng Sn/L. Diuron and Irgarol 1051, at concentration ranges of 35–1360 ng/L and nd to 14 ng/L, respectively, were the most common alternative biocides present in seawater, with the highest concentrations detected in fishing ports. Hot spots were identified where TBT levels exceeded environmental quality targets even 6 years after a total ban on its use in Korea. Diuron exceeded the UK environmental quality standard (EQS) value in 73% of the fishing port samples, 64% of the major bays, and 42% of the harbors. Irgarol 1051 levels were marginally below the Dutch and UK EQS values at all sites.     

Nutrients,irradiance, and mixing as factors regulating primary production in coastal waters impacted by the Mississippi River plume

Relationships among primary production, chlorophyll, nutrients, irradiance and mixing processes were examined along the salinity gradient in the Mississippi River outflow region. A series of six cruises were conducted during 1988–1992 at various times of year and stages of river discharge. Maximum values of biomass and primary production were typically observed at intermediate salinities and coincided with non-conservative decreases in nutrients along the salinity gradient. Highest values of productivity (>10 gC m⁻² d⁻¹) and biomass (>30 mg chlorophyll a m⁻³) were observed in April 1988, July–August 1990 and April–May 1992; values were lower in March and September 1991. Rates of primary production were apparently constrained by low irradiance and mixing in the more turbid, low salinity regions of the plume, and by nutrient limitation outside the plume. Highest values of primary production occurred at stations where surface nutrient concentrations exhibited large deviations from conservative mixing relationships, indicating that depletion of nutrients was related to phytoplankton uptake. Mixing and advection were important in determining the location and magnitude of primary production maxima and nutrient depletion. In addition to growth within plume surface waters, enhanced growth and/or retention of biomass may have occurred in longer residence time waters at the plume edge and/or beneath the surface plume. Vertical structure of some plume stations revealed the presence of subsurface biomass maxima in intermediate salinity water that was depleted in nutrients presumably by uptake processes. Exchange between subsurface water and the surface plume apparently contributed to the reduction in nutrients at intermediate salinities in the surface layer. DIN (=nitrate+nitrite+ammonium) : PO₄ (=phosphate) ratios in river water varied seasonally, with high values in winter and spring and low values in late summer and fall. Periods of high DIN : PO₄ ratios in river nutrients coincided with cruises when surface nutrient concentrations and their ratios indicated a high probability for P limitation. N limitation was more likely to occur at high salinities and during late summer and fall. Evidence for Si limitation was also found, particularly in spring.     

Selected trace metals (As,Cd and Hg) distribution and contamination in the coastal wetland sediment of the northern Beibu Gulf,South China Sea

Contamination with As, Cd and Hg, their spatial and temporal distribution are reported from the coastal wetland sediments of the northern Beibu Gulf, South China Sea. The content of As, Cd, Hg and TOC in surface sediments is 8.1 ± 5.8 μg g^?1, 0.08 ± 0.14 μg g^?1, 0.034 ± 0.028 μg g^?1 and 0.45 ± 0.39%, respectively. The mean sedimentation rates are 0.93–1.37 cm year^?1 during 1920s to 2008 determined by ²¹⁰Pb and ¹³⁷Cs dating in three cores. The vertical profiles of As, Cd and Hg content in the cores retrieved from Qin and Nanliu River estuaries show increasing trends during 1985–2008 due to anthropogenic impact caused by local economic development. Locally the surface sediments have potential ecological risk of As to benthos according to the NOAA sediment quality guidelines.     

Distribution and source apportionments of polychlorinated biphenyls (PCBs) in mariculture sediments from the Pearl River Delta,South China

Surface and core sediments collected from six mariculture farms in the Pearl River Delta (PRD) were analyzed to evaluate contamination levels of polychlorinated biphenyls (PCBs). The ∑PCBs (37 congeners) concentrations ranged from 5.10 to 11.0 ng g⁻¹ (mean 7.96 ng g⁻¹) in surface and 3.19 to 22.1 ng g⁻¹ (mean 7.75 ng g⁻¹) in core sediments, respectively. The concentrations were significantly higher than that measured in the sediments of their corresponding reference sites, whereby the average enrichment percentages were 62.0% and 42.7% in surface and core sediments, respectively. Significant correlations (R² = 0.77, p < 0.05) of PCB homologue group proportions between fish feeds and surface mariculture sediments suggested that fish feed input was probably the main source for the enrichment of PCBs. Due to the fact that PCBs could be transferred along food chains, PCB contamination in fish feeds and mariculture sediments should not be overlooked.     

Gas percolation in upper-crustal silicic crystal mushes as a mechanism for upward heat advection and rejuvenation of near-solidus magma bodies

Several crystal-rich, intermediate to silicic magmas erupted at arc volcanoes record a reheating event shortly prior to eruption: they provide evidence for remobilization of crystal mushes by mafic magmas. As hybridization between the mush and the mafic magma is often limited, bulk mixing could not be the dominant process in transferring heat. Conductive heating from a basaltic underplate plays a role, but a few characteristics of these rejuvenated mushes suggest that reheating occurs faster than predicted by conduction.In the upper crust, a process that can transport heat faster than conduction, and still remain chemically nearly imperceptible, is the upward migration of a hot volatile phase (“gas sparging”) that originates in underplated mafic magmas. Using numerical simulations, we quantified the thermal effects of two-phase flow (a silicic melt phase and a H₂O–CO₂ fluid phase) in the pore space of shallow silicic mushes that have reached their rheological lock-up point (i.e., rigid porous medium, crystallinity ≥ 50 vol.%). Results show that the reheating rates are significantly faster than conduction for volatile fluxes > 0.1 m³/m² yr. Considering that volatiles can be rapidly exsolved from the underplated mafic magma, these high fluxes can be promptly reached, leading to fast reheating; sill-like batches of mushes with volumes similar to the 1995–present eruption of the Soufrière Hills (Montserrat, W.I.) can be reheated by a few tens of degrees and remobilized within days to weeks. At these high fluxes, a considerable volume of volatiles is needed (similar to the volume of mush being reheated). Large silicic systems (> 100–1000 km³) require unrealistic amounts of volatiles to be reheated in a continuous, high-flux sparging event. Rejuvenation of batholithic mushes therefore requires multiple sparging episodes separated by periods dominated by near-conductive heat transfer at low-flux sparging (< 0.1 m³/m² yr) and may take up to 100–200 ky.