Distribution and bioaccumulation of polychlorinated biphenyls and organochlorine pesticides residues in sediments and Manila clams (Ruditapes philippinarum) from along the Mid-Western coast of Korea

The distribution and bioaccumulation features of PCBs, DDTs, and HCHs were investigated in the sediments and Manila clams collected from along the Mid-Western coast of Korea. The measured concentrations of ΣPCBs, ΣDDTs and ΣHCHs were 1.08–3.5, 0.12–0.35 and 0.090–0.30 ng g⁻¹ dw in sediment, and 33–390, 7.4–46 and 6.3–27 ng g⁻¹ lipid in Manila clam, respectively. Their levels were found to be relatively lower than those of other contaminated areas and the consumption of Manila clam from these areas seems to be safe for human health according to calculated lifetime cancer risk and hazard indices. The ΣPCBs and ΣDDTs concentrations in sediments showed a significant relationship to those in clams. The significant correlation was observed between BSAF in clams and K_ow for each PCB congeners and DDT metabolites. These findings support that the PCBs and DDTs levels, which are highly hydrophobic chemicals, in clam reflect the sediment pollution through bioaccumulation.     

Resistance of Lophelia pertusa to coverage by sediment and petroleum drill cuttings

In laboratory experiments, the cold-water coral Lophelia pertusa was exposed to settling particles. The effects of reef sediment, petroleum drill cuttings and a mix of both, on the development of anoxia at the coral surface were studied using O₂, pH and H₂S microsensors and by assessing coral polyp mortality. Due to the branching morphology of L. pertusa and the release of coral mucus, accumulation rates of settling material on coral branches were low. Microsensors detected H₂S production in only a few samples, and sulfate reduction rates of natural reef sediment slurries were low (<0.3 nmol S cm⁻³ d⁻¹). While the exposure to sediment clearly reduced the coral’s accessibility to oxygen, L. pertusa tolerated both partial low-oxygen and anoxic conditions without any visible detrimental short-term effect, such as tissue damage or death. However, complete burial of coral branches for >24 h in reef sediment resulted in suffocation.     

Baseline heavy metals and metalloid values in blood of loggerhead turtles (Caretta caretta) from Baja California Sur, Mexico

Environmental pollution due to heavy metals is having an increased impact on marine wildlife accentuated by anthropogenic changes in the planet including overfishing, agricultural runoff and marine emerging infectious diseases. Sea turtles are considered sentinels of ecological health in marine ecosystems. The objective of this study was to determine baseline concentrations of zinc, cadmium, copper, nickel, selenium, manganese, mercury and lead in blood of 22 clinically healthy, loggerhead turtles (Caretta caretta), captured for several reasons in Puerto López Mateos, Baja California Sur, Mexico. Zinc was the most prevalent metal in blood (41.89 μg g⁻¹), followed by Selenium (10.92 μg g⁻¹). The mean concentration of toxic metal Cadmium was 6.12 μg g⁻¹ and 1.01 μg g⁻¹ respectively. Mean concentrations of metals followed this pattern: Zn > Se > Ni > Cu > Mn > Cd > Pb and Hg. We can conclude that blood is an excellent tissue to measure in relatively non-invasive way baseline values of heavy metals in Caretta caretta.     

Morphological changes in branchial mitochondria-rich cells of the teleost Paralichthys olivaceus as a potential indicator of CO2 impacts

We studied the morphological and biochemical changes of mitochondria-rich cells (MRCs) of a demersal teleost, Paralichthys olivaceus, during exposure to 0.98, 2.97 and 4.95 kPa pCO₂. The apical opening area of MRCs increased 2.2 and 4.1 times by 24 h exposure to 2.97 and 4.95 kPa pCO₂, respectively, while the cross-sectional area or density of MRCs did not change. Gill Na⁺/K⁺-ATPase activity more than doubled at 72 h and then returned to the pre-exposure level at 168 h in 0.98 kPa pCO₂, while it increased 1.7 times at 24 h at 4.95 kPa. These results indicate that the apical opening area of MRCs and the gill Na⁺/K⁺-ATPase activity may be used as an indicator of acute (up to 72 h), but not chronic, impacts of high (>1 kPa) seawater CO₂ conditions in P. olivacues. Limitations of those parameters as indices of CO₂ impacts are discussed.     

Detection of nonylphenol and persistent organic pollutants in fish from the North Pacific Central Gyre

Despite scientific and public concern, research on food web contamination from chemicals in plastic is limited, and distinguishing plastic sources from prey remains a challenge. We analyzed juvenile yellowtail (Seriola lalandi) from the North Pacific Central Gyre for plastic ingestion and tissue concentrations of persistent organic pollutants and nonionic surfactants to investigate potential contamination from plastic exposure. Ingestion of synthetic debris occurred in ∼10% of the sample population. PCBs and DDTs were 352 ± 240 (mean ± SD) and 1425 ± 1118 ng/g lw, respectively. PBDEs were 9.08 ± 10.6 ng/g lw, with BDEs-47, 99, and 209 representing 90% of PBDEs. Nonylphenol (NP) was detected in one-third of the yellowtail with a mean of 52.8 ± 88.5 ng/g ww overall and 167 ± 72.3 ng/g ww excluding non-detects. Because environmental NP is strongly associated with wastewater treatment effluents, long-range transport is unlikely, and NP was previously measured in gyre plastic, we concluded that plastic-mediated exposure best explained our findings of NP in yellowtail.     

The influence of precipitate formation on the chemical oxidation of TCE DNAPL with potassium permanganate

A three-dimensional two-phase flow model is coupled to a non-linear reactive transport model to study the efficacy of potassium permanganate treatment on dense, non-aqueous phase liquid (DNAPL) source removal in porous media. A linear relationship between the soil permeability (k) and concentration of manganese dioxide precipitate ([MnO_2(s)]), k = k_o + S_rind [MnO_2(s)], is utilized to simulate nodal permeability reductions due to precipitate formation. Using published experimental column studies, an S_rind = −5.5 × 10⁻¹⁶ m² L/mg was determined for trichloroethylene (TCE) DNAPL. This S_rind was then applied to treatment simulations on three-dimensional TCE DNAPL source zones comprising either DNAPL at residual saturations, or DNAPL at pooled saturations.     

Effects of chronic exposure to dispersed oil on selected reproductive processes in adult blue mussels (Mytilus edulis) and the consequences for the early life stages of their larvae

Mussels (Mytilus edulis) were continuously exposed to dispersed crude oil (0.015-0.25 mg/l) for 7 months covering the whole gamete development cycle. After 1 month exposure to 0.25 mg oil/l, the level of alkali-labile phosphates (ALP) and the volume density of atretic oocytes in female gonads were higher than those in the gonads of control females, indicating that oil affected the level of vitellogenin-like proteins and gamete development. Spawning of mussels was induced after 7 months oil exposure. Parental oil exposure did not affect subsequent fertilization success in clean seawater but this was reduced in 0.25 mg oil/l. Parental exposure to 0.25 mg oil/l caused both slow development and a higher percentage of abnormalities in D-shell larvae 2 days post-fertilization; reduced growth 7 days post-fertilization. These effects were greatly enhanced when larval stages were maintained at 0.25 mg oil/l. Similar studies are warranted for risk assessment prognosis.     

Mercury bioaccumulation in the spotted dogfish (Scyliorhinus canicula) from the Atlantic Ocean

The annual and life-cycle mercury bioaccumulation pattern in selected tissues of the economically relevant Elasmobranchii species Scyliorhinus canicula was studied, and the risks associated with its consumption evaluated.Preferential mercury bioaccumulation occurred in muscle tissue, and followed the order muscle > heart > liver > gills > pancreas. Total mercury in muscle tissue ranged from 0.13 mg kg⁻¹ (wwt) in 1+ year old males to 0.8 mg kg⁻¹ (wwt) in 8+ year old mature females, with no significant differences found between genders, and no clear lifespan bioaccumulation pattern observed, except for mature females. Organic mercury in the muscle ranged from 0.05 mg kg⁻¹ (wwt) to 0.52 mg kg⁻¹ (wwt), corresponding to an average of 70% of total mercury content. In mature females, a significant correlation (R = 0.99, P = 0.01) was found between size and organic mercury fraction, suggesting reproduction as an important factor controlling organic mercury bioaccumulation in the spotted dogfish.     

Metamorphic effect on zircon Lu-Hf and U-Pb isotope systems in ultrahigh-pressure eclogite-facies metagranite and metabasite

The Hf isotope composition of original igneous or detrital zircons in high-grade metamorphic rocks can be used to trace protolith origin, but metamorphic effect on the Hf isotope composition of newly grown domains remains to evaluate. We report a detailed in situ combined study of intragrain U-Pb and Lu-Hf isotopes in zircons from granitic gneiss and eclogite in the Dabie orogen of China that experienced ultrahigh-pressure eclogite-facies metamorphism. The results show correlations in ²⁰⁶Pb / ²³⁸U age, initial Hf isotope composition, and Th / U and Lu / Hf ratios between the domains of different origins. The metamorphic domains are characterized by low Th / U and Lu / Hf ratios but high ?_Hf(t) values relative to the igneous core and mantle of pre-metamorphic ages. Positive correlations are observed between Th / U and Lu / Hf ratios, pointing to the similar effect of metamorphism on both U-Th-Pb and Lu-Hf isotope systems. Thus the metamorphic domains are distinguished from the igneous core and mantle by their low Lu / Hf ratios that are less than 0.001 for the granitic gneiss and less than 0.0001 for the eclogite. Despite differences in both protolith age and geochemical source between granitic gneiss and eclogite, rim ?_Hf(t) values are variably 3.1 to 13.5 greater than core ?_Hf(t) values when calculated at timing of protolith formation. This indicates that the zircon overgrowth was associated with a metamorphic medium that has high ¹⁷⁶Hf / ¹⁷⁷Hf but low ¹⁷⁶Lu / ¹⁷⁷Hf ratios. While the metamorphic domains contain more radiogenic Hf isotopes than the original igneous core and mantle, their Lu / Hf ratios are significantly lower than those of core and mantle. Therefore, the metamorphic zircons acquired their initial Hf isotope ratios from metamorphic fluids that have high ¹⁷⁶Hf / ¹⁷⁷Hf ratios but low Lu / Hf ratios with sound variability depending on the Lu-Hf isotope compositions of pre-existing and co-precipitating phases.     

Levels of persistent organic pollutants and residual pattern of DDTs in small cetaceans from the coast of São Paulo, Brazil

The State of São Paulo is the most developed area in Brazil and was impacted by persistent organic pollutants for several decades. This study investigated organochlorines in five species of small cetaceans (Pontoporia blainvillei, Stenella frontalis, Sotalia guianensis, Tursiops truncatus and Steno bredanensis) found dead along the coast of São Paulo between 1997 and 2003. DDTs (15.9 μg g⁻¹ lipid; mean for all pooled individuals) and PCBs (8.08 μg g⁻¹) exhibited the highest concentrations in the animals, reflecting large amounts formerly used in Brazil. Lower levels of mirex (0.149 μg g⁻¹), HCB (0.051 μg g⁻¹), CHLs (0.008 μg g⁻¹) and HCHs (0.007 μg g⁻¹) were detected in all species. Residual pattern of DDTs in dolphins suggests that o,p′-DDT is more recalcitrant than p,p′-DDT in the body of the animals and/or the environment. In contrast to p,p′-DDT, residues of o,p′-DDT seem to be preferentially converted into o,p′-DDD rather than o,p′-DDE.     

Bioconcentration of the anionic surfactant linear alkylbenzene sulfonate (LAS) in the marine shrimp Palaemonetes varians: A radiotracer study

Uptake and depuration kinetics of dissolved [¹⁴C]C₁₂-6-linear alkylbenzene sulfonate (LAS) were determined in the shrimp Palaemonetes varians using environmentally relevant exposure concentration. The shrimp concentrated LAS from seawater with a mean BCF value of 120 L kg⁻¹ after a 7-day exposure. Uptake biokinetics were best described by a saturation model, with an estimated BCF_ss, of 159 ± 34 L kg⁻¹, reached after 11.5 days. Shrimp weight influenced significantly BCF value with smaller individuals presenting higher affinity to LAS. To the light of a whole body autoradiography, major accumulation of LAS occurred in the cephalothorax circulatory system (gills, heart, hepatopancreas) and ocular peduncle, but not in the flesh, limiting potential transfer to human consumers. LAS depuration rate constant value of the shrimp was 1.18 ± 0.08 d⁻¹ leading to less than 1% of remaining LAS in its tissues after 8 days of depuration.     

Inter- and intra-annual patterns of Ulva prolifera green tides in the Yellow Sea during 2007-2009, their origin and relationship to the expansion of coastal seaweed aquaculture in China

The large green-tide events that occurred in the Yellow Sea in 2008 (3489 km²) and 2009 (4994 km²) are shown to be novel events preceded only once by a much smaller event in 2007 (82 km²). The blooms originated in the coastal area of Jiangsu province and spread north-east towards the Shandong Peninsula. The blooms grew at different rates and mesoscale variability in surface winds explained the differences in the spatial and temporal patterns of blooms in 2008 and 2009. The 2009 bloom was tracked to its origin immediately offshore of extensive intertidal flats between Yancheng and Nantong where recent rapid expansion of Porphyra aquaculture has occurred. We review published hypotheses which have been advanced to explain the occurrence of blooms and in light of our findings, we conclude that the accumulation and disposal of waste Ulva prolifera from Porphyra aquaculture rafts is the most likely cause of the blooms.     

Phytoplankton biomass and primary production responses to physico-chemical forcing across the northeastern New Zealand continental shelf

Phytoplankton biomass and primary production were monitored in the Hauraki Gulf and on the northeastern continental shelf, New Zealand - using ship surveys, moored instruments and satellite observations (1998-2001) - capturing variability across a range of space and time scales. A depth-integrated primary production model (DIM) was used to predict integrated productivity from surface parameters, enabling regional-specific estimates from satellite data. The shelf site was dominated by pico-phytoplankton, with low chlorophyll-a (<1 mg m⁻³) and annual production (136 g C m⁻² yr⁻¹). In contrast, the gulf contained a micro/nano-phytoplankton-dominated community, with relatively high chlorophyll-a (>1 mg m⁻³) and annual production (178 g C m⁻² yr⁻¹). Biomass and productivity responded to physico-chemical factors; a combination of light, critical mixing depths and/or nutrient limitation—particularly new nitrate-N. Relatively low biomass and production was observed during 1999. This coincided with inter-annual variability in the timing and extent of upwelling- and downwelling-favourable along-shelf wind-stress, influencing the fluxes of new nitrate-N to the shelf and gulf. Relationships with the Southern Oscillation Index are also discussed. Our multi-scaled sampling highlighted details associated with stratification and de-stratification events, and deep sub-surface chlorophyll-a not visible to satellite sensors. This study demonstrates the importance of multi-scaled sampling in gaining estimates of regional production and its responses to physico-chemical forcing.     

Prediction of Salmonella in seawater by total and faecal coliforms and Enterococci

The power of total coliforms (TC), faecal coliforms (FC) and Enterococci to predict the presence of Salmonella in seawater was investigated. Indicator cut-off values with the most satisfactory combination of sensitivity and specificity in predicting Salmonella presence were 1000 CFU 100 ml⁻¹ TC, 200 CFU 100 ml⁻¹ FC, 500 CFU 100 ml⁻¹ Enterococci. When TC or FC were used for Salmonella prediction in logistic regression, then the addition of another indicator did not have a statistically significant effect. When Enterococci were used for prediction, then the addition of either of the two other indicators led to a statistically significant improvement (P = 0.001 for TC, P = 0.003 for FC). These results suggest that using either TC or FC alone provided an adequate indicator of Salmonella presence, but a statistically significant improvement is possible over using Enterococci alone. Concerning Enterococci, European Union limits for excellent coastal water quality (100 CFU 100 ml⁻¹) and United States Environmental Protection Agency criteria for marine bathing waters (35 CFU 100 ml⁻¹) have the same value in predicting Salmonella absence (92.5%).     

Lead in blood and eggs of the sea turtle, Lepidochelys olivacea, from the Eastern Pacific: Concentration, isotopic composition and maternal transfer

Concentrations of lead were assessed in the sea turtle, Lepidochelys olivacea, from a nesting colony of the Eastern Pacific. Twenty-five female turtles were sampled and a total of 250 eggs were collected during the “arribada” event of the 2005-2006 season. Considering the nesting season, the maternal transfer of lead (Pb) via egg-laying, in terms of metal burden in whole body, was 0.5%. Pb concentrations (in dry weight) in blood (0.95 ± 0.18 μg g⁻¹) and egg samples (yolk, 0.80 ± 0.10 μg g⁻¹; albumen, 1.08 ± 0.20 μg g⁻¹; eggshell, 1.05 ± 0.20 μg g⁻¹) were comparable or even lower than those found in other sea turtles. The isotope ratios (²⁰⁶Pb/²⁰⁷Pb and ²⁰⁶Pb/²⁰⁸Pb) in blood (1.183 ± 0.0006 and 2.452 ± 0.0006, respectively) were comparable to that of natural Pb-bearing bedrock in Mexico (1.188 ± 0.005 and 2.455 ± 0.008, respectively). According to international norms of Pb, the health of this population and its habitats is acceptable for Pb and corresponds to basic levels of a nearly pristine environment.     

Iron isotope fractionation during planetary differentiation

The Fe isotope composition of samples from the Moon, Mars (SNC meteorites), HED parent body (eucrites), pallasites (metal and silicate) and the Earth's mantle were measured using high mass resolution MC-ICP-MS. These high precision measurements (δ⁵⁶Fe ≈ ± 0.04‰, 2 S.D.) place tight constraints on Fe isotope fractionation during planetary differentiation.Fractionation during planetary core formation is confined to < 0.1‰ for δ⁵⁶Fe by the indistinguishable Fe isotope composition of pallasite bulk metal (including sulfides and phosphides) and olivine separates. However, large isotopic variations (≈ 0.5‰) were observed among pallasite metal separates, varying systematically with the amounts of troilite, schreibersite, kamacite and taenite. Troilite generally has the lightest (δ⁵⁶Fe ≈ − 0.25‰) and schreibersite the heaviest (δ⁵⁶Fe ≈ + 0.2‰) Fe isotope composition. Taenite is heavier then kamacite. Therefore, these variations probably reflect Fe isotope fractionation during the late stage evolution and differentiation of the S- and P-rich metal melts, and during low-temperature kamacite exsolution, rather than fractionation during silicate-metal separation.Differentiation of the silicate portion of planets also seems to fractionate Fe isotopes. Notably, magmatic rocks (partial melts) are systematically isotopically heavier than their mantle protoliths. This is indicated by the mean of 11 terrestrial peridotite samples from different tectonic settings (δ⁵⁶Fe = + 0.015 ± 0.018‰), which is significantly lighter than the mean of terrestrial basalts (δ⁵⁶Fe = + 0.076 ± 0.029‰). We consider the peridotite mean to be the best estimate for the Fe isotope composition of the bulk silicate Earth, and probably also of bulk Earth. The terrestrial basaltic mean is in good agreement with the mean of the lunar samples (δ⁵⁶Fe = + 0.073 ± 0.019‰), excluding the high-Ti basalts. The high-Ti basalts display the heaviest Fe isotope composition of all rocks measured here (δ⁵⁶Fe ≈ + 0.2‰). This is interpreted as a fingerprint of the lunar magma ocean, which produced a very heterogeneous mantle, including the ilmenite-rich source regions of these basalts.Within uncertainties, samples from Mars (SNC meteorites), HED (eucrites) and the pallasites (average olivine + metal) have the same Fe isotope compositions as the Earth's mantle. This indicates that the solar system is very homogeneous in Fe isotopes. Its average δ⁵⁶Fe is very close to that of the IRMM-014 standard.     

Quality assessment of the blue mussel (Mytilus edulis): Comparison between commercial and wild types

This study compared species identity, microplastics, chemical and microbial contamination between consumption mussels and wild type mussels, collected at Belgian department stores and Belgian groynes and quaysides, respectively. Species identification based on genetic analysis showed a high number of Mytilus (M.) edulis compared to M. galloprovincialis and M. edulis/galloprovincialis hybrid mussels. The number of total microplastics varied from 2.6 to 5.1 fibres/10 g of mussel. A higher prevalence of orange fibres at quaysides is related to fisheries activities. Chemical contamination of polycyclic aromatic hydrocarbons and polychlorobiphenyls could be related to industrial activities and water turbidity, with maximum concentrations at the quayside of port Zeebrugge. The inverse was noted for Escherichia coli contamination, which was relatively low at Zeebrugge quayside with a total count of 3.9 × 10² CFU/100 g tissue, due to limited agricultural effluents. Results of this complementary analysis stress the importance of integrated monitoring and quality assessment.     

Mixed memory, (non) Hurst effect, and maximum entropy of rainfall in the tropical Andes

Diverse linear and nonlinear statistical parameters of rainfall under aggregation in time and the kind of temporal memory are investigated. Data sets from the Andes of Colombia at different resolutions (15 min and 1-h), and record lengths (21 months and 8-40 years) are used. A mixture of two timescales is found in the autocorrelation and autoinformation functions, with short-term memory holding for time lags less than 15-30 min, and long-term memory onwards. Consistently, rainfall variance exhibits different temporal scaling regimes separated at 15-30 min and 24 h. Tests for the Hurst effect evidence the frailty of the R/S approach in discerning the kind of memory in high resolution rainfall, whereas rigorous statistical tests for short-memory processes do reject the existence of the Hurst effect.Rainfall information entropy grows as a power law of aggregation time, S(T) ∼ T^β with 〈β〉 = 0.51, up to a timescale, T_MaxEnt (70-202 h), at which entropy saturates, with β = 0 onwards. Maximum entropy is reached through a dynamic Generalized Pareto distribution, consistently with the maximum information-entropy principle for heavy-tailed random variables, and with its asymptotically infinitely divisible property. The dynamics towards the limit distribution is quantified. Tsallis q-entropies also exhibit power laws with T, such that S_q(T) ∼ T^β(q), with β(q) ? 0 for q ? 0, and β(q) ? 0.5 for q ? 1. No clear patterns are found in the geographic distribution within and among the statistical parameters studied, confirming the strong variability of tropical Andean rainfall.     

Effects of lanthanum(III) and EDTA on the growth and competition of Microcystis aeruginosa and Scenedesmus quadricauda

Rare earth elements (REEs) are widely used to increase crop production in China. However, little attention has been paid to their impacts on aquatic ecology. Batch cultivation was used here to study the effects of lanthanum (La) and EDTA on the growth and competition of the cyanobacterium Microcystis aeruginosa and the green alga Scenedesmus quadricauda. When EDTA was present at a very low concentration (0.269 μmol L⁻¹), low lanthanum concentrations (?7.2 μmol L⁻¹) had little stimulative effect on the growth of M. aeruginosa and S. quadricauda, whereas a high lanthanum concentration (72 μmol L⁻¹) had significant inhibitory effect on both of them. The results of cultivation experiments suggested that the inhibitory effect on M. aeruginosa was higher than that on S. quadricauda and S. quadricauda could become dominant in mixed cultures. When lanthanum was not added to the culture medium, high EDTA concentrations (>13.4 μmol L⁻¹) had a great inhibitory effect on the growth of M. aeruginosa but little effect on the growth of S. quadricauda, which could become dominant in the mixed cultures.Lanthanum and EDTA had complex effects on the growth and competition of M. aeruginosa and S. quadricauda. EDTA did not change the stimulation of low lanthanum concentrations on both, but at intermediated concentrations (2.69-13.4 μmol L⁻¹) it could greatly alleviate lanthanum inhibition on M. aeruginosa; thus, M. aeruginosa would dominate S. quadricauda in these mixed cultures. Lanthanum at low concentration (7.2 μmol L⁻¹) could also alleviate the inhibition of high EDTA on M. aeruginosa, but did not alter the outcome of the competition.     

Ostreopsis cf. ovata bloom in the northern Adriatic Sea during summer 2009: ecology, molecular characterization and toxin profile

Intense blooms of the benthic dinoflagellate Ostreopsis cf. ovata have occurred in the northern Adriatic Sea since 2006. These blooms are associated with noxious effects on human health and with the mortality of benthic organisms because of the production of palytoxin-like compounds. The O. cf. ovata bloom and its relationships with nutrient concentrations at two stations on the Conero Riviera (northern Adriatic Sea) were investigated in the summer of 2009. O. cf. ovata developed from August to November, with the highest abundances in September (1.3 × 10⁶ cells g⁻¹ fw corresponding to 63.8 × 10³ cells cm⁻²). The presence of the single O. cf. ovata genotype was confirmed by a PCR assay. Bloom developed when the seawater temperature was decreasing. Nutrient concentrations did not seem to affect bloom dynamics. Toxin analysis performed by high resolution liquid chromatography-mass spectrometry revealed a high total toxin content (up to 75 pg cell⁻¹), including putative palytoxin and all the ovatoxins known so far.