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In this work, the effect of γ-radiation on the decomposition of adenine dissolved in distilled water, saline solutions and artificial seawater was studied. As the composition of the major cations and anions of artificial seawater probably better resembles the composition of seawater on the Earth 4.0 billion years ago, this seawater was named artificial seawater 4.0 Ga. The main finding in this work is that artificial seawater 4.0 Ga demonstrated a better protective effect of adenine against γ-radiation. In addition, artificial seawater 4.0 Ga showed that adenine had no changes in pH after radiation exposure and the minor radiation-chemical yield G. The radiolysis of adenine promoted modifications in Fourier-transform infrared spectra. The deconvolution of some bands demonstrated the formation of a new frequency at 1713 cm−1. High performance liquid chromatography-mass detected a product of decomposition with 151 atomic units. Using the geometry optimization and simulated vibrational spectra it was possible to show that the main species formed are hydroxyl and oxide modified adenine. The data point to the formation of hydroxyl-adenine and adenine Nx-oxide. These products have biological relevance and could be available for chemical evolution.
A new method to extract CO2 in seawater samples for the determination of F14C has been developed in the Laboratory of Ion Beam Physics at ETH Zurich. The setup consists of an automated sampler designed to extract dissolved inorganic carbon (DIC) from 7 samples in a row, by flushing the seawater with He gas to extract CO2. The fully automated method is controlled via a LabVIEW program that runs through all consecutive steps: catalyst preconditioning, CO2 extraction, CO2 trapping, thermal CO2 release from the trap into the reactor and finally the graphitization reaction which is performed simultaneously in the 7 reactors. The method was optimized by introducing a Cu-Ag furnace that was placed between the water and zeolite traps, which resulted in a better and faster graphitization performance (<2 hr) compared to previously used techniques. The method showed to be reproducible with an unprecedented precision of 1.7‰ even though consuming only 50–60 mL of seawater. The high throughput of 21 samples per day allows for coverage of future oceanographic transects with high spatial resolution, thus fostering the use of radiocarbon (14C) as water mass tracer.
Surface radiocarbon (Δ14C) in the North Pacific has been monitored using a commercial volunteer observation ship since the early 2000s. Here we report the temporal and spatial variations in Δ14C in the summer surface water when the surface ocean is vertically stratified over a 13-yr period, 2004–2016. The long-term Δ14C decreasing trend after the late 1970s in the subtropical region has continued to the present and the rate of decrease of the Kuroshio and Kuroshio Extension, North Pacific and California current areas is calculated to be –3.3, –5.2 and –3.3 ‰/yr, respectively. After 2012 the Δ14C of the Kuroshio and Kuroshio Extension area, however, has remained at an approximately constant value of around 50‰. The result may indicate that subtropical surface Δ14C in the western North Pacific has reached an equilibrium with atmospheric Δ14CO2. The Δ14C in the subarctic region is markedly lower than values in the subtropical region and it seems that the decreasing tendency of surface Δ14C has changed to an increasing tendency after 2010. The results may indicate that bomb-produced 14C, which has accumulated below the mixed layer in the past few decades, has been entrained into the surface layer by deep convection.
The first ultraviolet photochemical oxidation (UVox) extraction method for marine dissolved organic carbon (DOC) as CO2 gas was established by Armstrong and co-workers in 1966. Subsequent refinement of the UVox technique has co-evolved with the need for high-precision isotopic (Δ14C, δ13C) analysis and smaller sample size requirements for accelerator mass spectrometry radiocarbon (AMS 14C) measurements. The UVox line at UC Irvine was established in 2004 and the system reaction kinetics and efficiency for isolating seawater DOC rigorously tested for quantitative isolation of ∼1 mg C for AMS 14C measurements. Since then, improvements have been made to sampling, storage, and UVox methods to increase overall efficiency. We discuss our progress, and key UVox system parameters for optimizing precision, accuracy, and efficiency, including (1) ocean to reactor: filtration, storage and preparation of DOC samples, (2) cryogenic trap design, efficiency and quantification of CO2 break through, and (3) use of isotopic standards, blanks and small sample graphitization techniques for the correction of DOC concentrations and Fm values with propagated uncertainties. New DOC UVox systems are in use at many institutions. However, rigorous assessment of quantitative UVox DOC yields and blank contributions, DOC concentrations and carbon isotopic values need to be made. We highlight the need for a community-wide inter-comparison study.
The adsorption and desorption of cesium onto layered minerals, zeolite and geochemical reference samples were studied. 0.5 g of bentonite and mica were able to adsorb 71.2 and 51.5 mg of cesium, respectively, from 50 mL of deionized water containing 200 mg/L of cesium under neutral pH condition. These amounts of cesium adsorption were greater than those reported for vermiculites (8.9 and 5.6 mg, respectively). Additionally, the cesium adsorption on mica and vermiculite remained essentially unchanged under seawater conditions, but it decreased drastically on zeolite. The cesium desorption from the layered minerals was promoted by the addition of ammonium ions, namely trioctylmethylammonium chloride and zephiramine. These ammonium ions desorb cesium from the interlayers of the minerals without destroying the mineral structure. The cesium desorption procedure using quaternary ammonium ions would be extremely useful for decontamination of soil containing the layered minerals with adsorbed radioactive cesium.
Global warming is facilitating the poleward range expansion of plant and animal species. In the Mediterranean Sea, the concurrent temperature increase and abundance of (sub)tropical non-indigenous species (NIS) is leading to the so-called ‘tropicalization’ of the Mediterranean Sea, which is dramatically evident in the south-eastern sectors of the basin. At the same time, the colder north-western sectors of the basin have been said to undergo a process of ‘meridionalization’, that is the establishment of warm-water native species (WWN) previously restricted to the southern sectors. The Gulf of Genoa (Ligurian Sea) is the north-western reach for southern species of whatever origin in the Mediterranean. Recent (up to 2015) observations of NIS and WWN by diving have been collated to update previous similar inventories. In addition, the relative occurrences of both groups of southern species have been monitored by snorkelling between 2009 and 2015 in shallow rocky reefs at Genoa, and compared with the trend in air and sea surface temperatures. A total of 20 southern species (11 NIS and 9 WWN) was found. Two WWN (the zebra seabream Diplodus cervinus and the parrotfish Sparisoma cretense) and three NIS (the SW Atlantic sponge Paraleucilla magna, the Red Sea polychaete Branchiomma luctuosum, and the amphi-American and amphi-Atlantic crab Percnon gibbesi) are new records for the Ligurian Sea, whereas juveniles of the Indo-Pacific bluespotted cornetfish Fistularia commersonii have been found for the first time. While temperature has kept on increasing for the whole period, with 2014 and 2015 being the warmest years since at least 1950, the number of WWN increased linearly, that of NIS increased exponentially, contradicting the idea of meridionalization and supporting that of tropicalization even in the northern sectors of the Mediterranean basin.
The standard procedure for storing/preserving seawater dissolved organic carbon (DOC) samples after field collection is by freezing (–20°C) until future analysis can be made. However, shipping and receiving large numbers of these samples without thawing presents a significant logistical problem and large monetary expense. Access to freezers can also be limited in remote field locations. We therefore test an alternative method of preserving and storing samples for the measurement of DOC concentrations ([DOC]), stable carbon (δ13C), and radiocarbon (as ∆14C) isotopic values via UV photooxidation (UVox). We report a total analytical reproducibility of frozen DOC samples to be [DOC]±1.3 µM, ∆14C±9.4‰, and δ13C±0.1‰, comparable to previously reported results (Druffel et al. 2013). Open Ocean DOC frozen versus acidified duplicates were on average offset by ∆DOC±1.1 µM, ∆∆14C± –1.3‰, and ∆δ13C± –0.1‰. Coastal Ocean frozen vs. acidified sample replicates, collected as part of a long-term (380-day) storage experiment, had larger, albeit consistent offsets of ∆DOC±2.2 µM, ∆∆14C±1.5‰, and ∆δ13C± –0.2‰. A simple isotopic mass balance of changes in [DOC], ∆14C, and δ13C values reveals loss of semi-labile DOC (2.2±0.6 µM, ∆14C=–94±105‰, δ13C=–27±10‰; n=4) and semi-recalcitrant DOC (2.4±0.7 µM, ∆14C=–478±116‰, δ13C=–23.4±3.0‰; n=3) in Coastal and Open Ocean acidified samples, respectively.
The nutritional requirement for n-3 long-chain PUFA in fast-growing Atlantic salmon (Salmo salar) during grow out in the sea is not well documented. Diets were formulated with levels of EPA (20 : 5n-3) and DHA (22 : 6n-3) ranging from 1·3 to 7·4 % of fatty acids (4–24 g/kg feed). Two long-term trials were conducted through the seawater phase, the first at 6 and 12°C, and the second at 12°C. In the first trial, growth at both temperatures was significantly lower in fish fed 1·4 % EPA+DHA of total fatty acids compared with the 5·2 % EPA+DHA group. In the second trial, growth was significantly lower in fish fed 1·3 and 2·7 % compared with 4·4 and 7·4 % EPA + DHA. Fatty acid composition in the fish reflected diet composition, but only after a 7-fold increase in body weight did the fatty acid profile of the fish stabilise according to dietary fatty acids (shown for EPA and DHA). The retention efficiency of DHA increased with decreasing dietary levels, and was 120–190 and 120–200 % in trials 1 and 2, respectively. The retention efficiency of EPA was lower (60–200 %), and values >100 % were only achieved at the lowest dietary levels in both trials. Temperature did not affect fatty acid retention efficiency. These results suggest that Atlantic salmon have a specific requirement for EPA + DHA >2·7 % of fatty acids for optimal long-term growth in seawater, and that short-term growth trials with less weight increase would not show these effects.
Over 300 million people rely on desalinated seawater and the numbers are growing. Desalination removes iodine from water and could increase the risk of iodine-deficiency disorders (IDD). The present study assessed the relationship between iodine intake and thyroid function in an area reliant on desalination.
A case–control study was performed between March 2012 and March 2014. Thyroid function was rigorously assessed by clinical examination, ultrasound and blood tests, including serum thyroglobulin (Tg) and autoimmune antibodies. Iodine intake and the contribution made by unfiltered tap water were estimated by FFQ. The contribution of drinking-water to iodine intake was modelled using three iodine concentrations: likely, worst-case and best-case scenario.
The setting for the study was a hospital located on the southern Israeli Mediterranean coast.
Adult volunteers (n 102), 21–80 years old, prospectively recruited.
After screening, seventy-four participants met the inclusion criteria. Thirty-seven were euthyroid controls. Among those with thyroid dysfunction, twenty-nine were classified with non-autoimmune thyroid disease (NATD) after excluding eight cases with autoimmunity. Seventy per cent of all participants had iodine intake below the Estimated Average Requirement (EAR) of 95 µg/d. Participants with NATD were significantly more likely to have probable IDD with intake below the EAR (OR=5·2; 95 % CI 1·8, 15·2) and abnormal serum Tg>40 ng/ml (OR=5·8; 95 % CI 1·6, 20·8).
Evidence of prevalent probable IDD in a population reliant on desalinated seawater supports the urgent need to probe the impact of desalinated water on thyroid health in Israel and elsewhere.
The adsorption of amino acids onto minerals in prebiotic seas may have played an important role for their protection against hydrolysis and formation of polymers. In this study, we show that the adsorption of the prebiotic amino acids, glycine (Gly), α-alanine (α-Ala) and β-alanine (β-Ala), onto Na+-montmorillonite was dependent on salinity and pH. Specifically, adsorption decreased from 58.3–88.8 to 0–48.9% when salinity was increased from 10 to 100–150% of modern seawater. This result suggests reduced amino acid adsorption onto minerals in prebiotic seas, which may have been even more saline than the tested conditions. Amino acids also formed complexes with metals in seawater, affecting metal adsorption onto Na+-montmorillonite, and amino acid adsorption was enhanced when added before Na+-montmorillonite was exposed to high saline solutions. Also, the dissolution of Na+-montmorillonite was reduced in the presence of amino acids, with β-Ala being the most effective. Thus, prebiotic chemistry experiments should also consider the integrity of minerals in addition to their adsorption capacity.
The concentrations of organophosphoric acid triesters (OPEs) in water samples from Maizuru Bay were in the range of 3.0–62 ng/l. In general, the concentrations of OPEs were found in the order of TBXP > TDCPP > TCEP > TBP > TCP > TPP > TEP. The organophosphorous pesticides (OPPs) diazinon, fenitrothion, iprobenfos and chlorpyrifos were detected in water samples. The concentrations of OPEs in sediment from Maizuru Bay were in the range of <0.5–56 µg kg−1 dry weight (dw). Among OPPs, diazinon in sediment samples were in the range of 1.8–71 µg kg−1 dw. However, the detection frequencies of fenitrothion and chlorpyrifos in sediment were low. The concentrations of OPEs in mussels from Maizuru Bay were in the range of <1–34 µg kg−1 wet weight (ww). The concentrations of OPEs were found in the order of TBP > TDCPP > TCP > TBXP = TPP = TCEP. Pesticides were detected in mussels, but these concentrations were lower than the acceptable daily intake (ADI) values. The partition coefficients between water and sediment (Kws) of diazinon and fenitrothion were 200–1300 and 200–300, respectively and the partition coefficients between water and biological samples (Kwb) of diazinon and fenitrothion were 700–3300 and 450–700, respectively, suggesting that these pesticides accumulate in biological samples at higher rates than in sediment.
Many adverse environmental factors influencing the Shatt-al Arab River, southern Iraq, during the past century and especially in recent years, combined with the ever-increasing demand for freshwater in the region, indicate the need to obtain information about its salinity regime. The aim of our study was both to find out what historical data there are and then to compare these with the results of a survey of the salinity and water quality of a stretch of the present river over the year October 2009–September 2010. The evidence suggests that there has been a marked upstream shift in the influence of sea water. Salinity values of 2 and 8‰ were found at two sites where elevated salinity had never been reported previously. Water quality variables indicated increased concentrations over the previous four decades and were beyond the national and international standards. As such changes in a major water resource have serious implications for the inhabitants of Basrah, the biological diversity in the river and the whole Gulf ecosystem, it is suggested that there should be a much more detailed study to provide the evidence needed to convince upstream water users of the need to conserve water and manage the whole catchment properly.
The technological development of all kinds of lightweight transportation devices including vehicles, aircraft, ships, etc. has progressed markedly with the demand for energy saving and environmental protection. Aluminum alloy is in the spotlight as it is a suitable environmentally friendly material. However, deformation is a major problem during the welding process because aluminum alloy has a large thermal expansion coefficient. In addition, it is known that its corrosion resistance is excellent; nevertheless, in practice, considerable corrosion is generated and this is a major problem. To solve this problem, the friction stir welding (FSW) technology is applied extensively at various industrial fields as a new welding technique. This method involves a process in which materials are joined by frictional heat and physical force. Therefore, we evaluated improvements in mechanical properties and corrosion resistance through annealing heat treatment after FSW. The electrochemical experiment did not show a significant difference. However, the microstructure observation showed defectless, fine crystal particles, indicating excellent properties at 200–225°C.
In the present work, the interactions between forsterite-91 with distilled water and forsterite-91 with artificial seawater were studied at two pHs (2.0 and 8.0) using different techniques. A large increase in pH was observed for samples incubated at an initially acidic pH (2.0) due to the dissolution of forsterite-91 in distilled water and artificial seawater. Thus, in acidic hydrothermal vents, an increase in the amount of hydrocarbons and magnetite should be expected due to the release of Fe(II). The pHPZC decreased and the pHIEP increased when forsterite-91 was treated with distilled water and artificial seawater. The ions from the artificial seawater had an effect on zeta potential. Scanning electron microscopy (SEM) images and X-ray diffractograms showed halite in the samples of forsterite-91 mixed with artificial seawater. The presence of halite or adsorption of ions on the surface of forsterite-91 could affect the synthesis of magnetite and hydrocarbons in hydrothermal vents, due to a decrease in the dissolution rates of forsterite-91. The dissolution of forsterite-91 yields low concentrations of Fe(III) and Mn(II) as detected by electron paramagnetic resonance (EPR) spectroscopy. Microanalysis of forsterite-91 showed a higher amount of Mn, with an oxidation that was likely not +II, as Mn in supernatant solutions was only detected by EPR spectroscopy after mixing with artificial seawater at pH 2.0. As Fe(III) and Mn(II) are catalyst constituents of magnetite and manganese oxide, respectively, their presence is important for synthesis in hydrothermal vents. Etch pits were observed only in the forsterite-91 sample mixed with distilled water at pH 8.0. Na, Cl, S, Ca and K were detected in the samples mixed with artificial seawater by SEM–EDS. Si, Mg, Fe and Al were detected in almost all supernatant samples due to forsterite-91 dissolution. Cr was not dissolved in the experiments, thus Cr in the mineral could serve as an effective catalyst for Fischer Tropsch Types (FTT) reactions in hydrothermal vent systems. X-ray diffractograms of the original forsterite-91 also showed peaks arising from zeolites and clinochlore. After the samples were treated with artificial seawater, X-ray diffractograms showed the dissolution of zeolite. Experiments should be performed in the natural environment to verify the potential for zeolites to act as a catalyst in hydrothermal vents.
This study investigated the synthesis of goethite under conditions resembling those of the prebiotic Earth. The artificial seawater used contains all the major elements as well as amino acids (α-Ala, β-Ala, Gly, Cys, AIB) that could be found on the prebiotic Earth. The spectroscopic methods (FT-IR, EPR, Raman), scanning electron microscopy (SEM) and X-ray diffraction showed that in any condition Gly and Cys favoured the formation of goethite, artificial seawater plus β-Ala and distilled water plus AIB favoured the formation of hematite and for the other synthesis a mixture of goethite and hematite were obtained. Thus in general no protein amino acids (β-Ala, AIB) favoured the formation of hematite. As shown by surface enhanced Raman spectroscopy (SERS) spectra the interaction between Cys and Fe3+ of goethite is very complex, involving decomposition of Cys producing sulphur, as well as interaction of carboxylic group with Fe3+. SERS spectra also showed that amino/CN and C-CH3 groups of α-Ala are interacting with Fe3+ of goethite. For the other samples the shifting of several bands was observed. However, it was not possible to say which amino acid groups are interacting with Fe3+. The pH at point of zero charge of goethites increased with artificial seawater and decreased with amino acids. SEM images showed when only goethite was synthesized the images of the samples were acicular and when only hematite was synthesized the images of the samples were spherical. SEM images for the synthesis of goethite with Cys were spherical crystal aggregates with radiating acicular crystals. The highest resonance line intensities were obtained for the samples where only hematite was obtained. Electron paramagnetic resonance (EPR) and Mössbauer spectra showed for the synthesis of goethite with artificial seawater an isomorphic substitution of iron by seawater cations. Mössbauer spectra also showed that for the synthesis goethite in distilled water plus Gly only goethite was synthesized and in artificial seawater plus Cys a doublet due to interaction of iron with artificial seawater/Cys was observed. It should be pointed out that EPR spectroscopy did not show the interaction of iron with artificial seawater/Cys.
The accident at the Fukushima Dai-ichi Nuclear Power Plant (FDNPP) in March 2011 led to
an unprecedented direct input of artificial radioactivity into the marine environment. The
Institute for Radioprotection and Nuclear Safety was requested by the French authorities
to investigate the radioecological impact of this input, in particular the potential
contamination of products of marine origin used for human consumption. This article
describes the close link between the responses provided and the availability of the data,
as well as their nature and ability to meet the requirements of expert investigation.
These responses were needed: (i) to evaluate the inputs of radionuclides into the marine
environment, (ii) to understand their dispersion in seawater, and (iii) to estimate their
transfer to the biota and sediments. Three phases can be distinguished which characterise
these processes during the accident and post-accident periods. The first phase corresponds
to an emergency phase during which no measurements were available on samples from the
marine environment. It involved the formulation of hypotheses based solely on the
expertise of the Institute for Radioprotection and Nuclear Safety. The second phase
started when the Japanese authorities provided measurements of the concentrations of
radionuclides in seawater. Although these data were not yet adapted to addressing the
problems of radioecology, the scenarios could then be refined and the estimates developed
in more detail. During the third phase, the accumulation of data over the course of time
made it possible to study the phenomena in an appropriate way. The chronology of the
events shows that it is essential to have (i) significant measurements of concentration
from samples collected in the various matrices of the marine environment, regularly
updated and sufficiently well-documented, (ii) samples of seawater collected at the
earliest opportunity as close as possible to the damaged site to characterise the source
term, and (iii) a numerical tool allowing rapid modelling of the dispersion of
radionuclides in seawater, as well as their transfer to sediments and the biota,
ultimately for the purpose of estimating the dose to humans.
Since contradictory data can be found in the literature, it is often difficult to assess the susceptibility of crevice corrosion of stainless steels in service conditions for a given marine application. The initiation and propagation of crevice corrosion in natural seawater were evaluated for five different duplex stainless steel grades together with some austenitic grades. A CREVCORR-type assembly was used to simulate crevice configurations involving the use of plastic crevice formers. The standard pressure applied on the crevice assembly was 3 N/mm2. Pressure of about 20 N/mm2 was also applied on some selected specimens in order to assess the effect of crevice geometry on crevice corrosion. The effect of environmental parameters (i.e. temperature, flowing conditions, residual chlorine, and dissolved oxygen content) and of surface roughness on the crevice corrosion initiation and propagation were investigated, allowing the assessment of limits of applications for some tested stainless steel grades. The less alloyed duplex stainless steels were evaluated in stagnant seawater at 5 °C and 20 °C. The duplex stainless steel UNS S32205, with PREN = 37, was also evaluated under the same conditions of exposure. The high alloyed stainless steels with PREN above 40 were evaluated in the expected most severe conditions of exposure, namely in 0.5 ppm-chlorinated seawater at 20 °C, in seawater at 30 °C (not chlorinated and with 0.5 ppm of residual chlorine) and in seawater at 50 °C (not chlorinated and with 0.5 ppm of residual chlorine). As expected the less alloyed duplex stainless steels showed limited crevice corrosion resistance in the tested media while UNS S32205 showed better resistance in the less severe tested condition of exposure. In demanding media it was shown that the limits of application of highly alloyed stainless steels are highly dependent on the crevice geometry (i.e. specimen roughness and applied pressure at gasket location).
An investigation of the latitudinal distribution of concentrations
of 137Cs at 19 stations in the surface water of the Southern
Ocean on cross-sections to the South from the Cape of Good Hope
(section SR2) and in the Drake Passage (30th cruise "Academic Ioffe",
01.12.2009–09.01.2010) was performed. The data obtained reinforced
the time-dependent exponential decrease in the 137Cs
concentrations in the surface water of the Atlantic sector of the
Southern Ocean. Increased 137Cs concentrations were found
in the Drake Passage and in the section SR2 in the vicinity of the
Polar Front. The average value of 137Cs concentrations
for all measurements equals 0.18 Bq.m–3 σ = 0.11.
During the 2007–08 Spanish Antarctic campaign, two moorings of bottom pressure sensors were carried out over a ten week period. This paper presents the results of the tidal analysis from sea level records obtained at Deception and Livingston islands (South Shetland Islands, Antarctica). The main objective of this paper is to present a detailed study of the tidal characteristics at these two islands, for which statistical and harmonic analysis techniques are applied to the tidal records. A geodetic network was used to reference the pressure sensors. Geometric levelling, with an accuracy of 1 mm, allowed us to link the tidal marks with geodetic vertices located on Livingston and Deception islands. The amplitudes and phase lags obtained by harmonic analysis are compared to the harmonic constants of several coastal stations and co-tidal and co-range charts. Results show an evident influence of tides in the sea level signal, with a clear mixed semi-diurnal behaviour and a daily inequality between high and low waters. Measurements of salinity and temperature were made using electronic sensors. Results from this study showed that salinity and temperature were strongly influenced by tides. Seawater temperature varied in a manner that was consistent with the time series of residual bottom pressure.
Phylogenetic analyses of SSU rDNA sequences have previously revealed the existence of 2 Ichthyobodo species able to infect Atlantic salmon (Salmo salar L.). Ichthyobodo necator sensu stricto (s.s.) is assumed to be a freshwater parasite, while a genetically distinct but undescribed species, Ichthyobodo sp. II sensu Todal et al. (2004) have been detected on Atlantic salmon in both fresh- and seawater. In the present study a morphological description of Ichthyobodo sp. II from the gills of salmon reared in fresh-, brackish- and seawater is presented, using both light- and electron microscopy. Comparative morphometry show that Ichthyobodo sp. II from both freshwater and seawater displays a different cell shape, and is significantly smaller than I. necator s.s. Also, ultrastructural characteristics distinguish these two species, notably differences in the attachment region and the presence of spine-like surface projections in Ichthyobodo sp. II. Based on both unique SSU rDNA sequences and morphological characteristics, we conclude that Ichthyobodo sp. II. represents a novel species for which we propose the name Ichthyobodo salmonis sp. n.