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The present study aims to compare the toxicity effect of Copper and Irgarol 1051 as antifouling agents on metabolites products in marine algae Dunaliella salina. Different concentrations of Cu (5, 15 & 25 mg/l) and Irgarol 1051 (0.012, 0.025 & 0.050 μg/l) were laboratories prepared and their impacts on growth, protein, and carbohydrates in Dunaliella salina were tested. Selections of these concentrations were initiated based on the response of the studied alga which had slightly or marked effects on its growth, and also to avoid the non-effective and directly lethal concentrations on the experimented alga. The obtained results showed stimulation in the growth of algae under the effect of the lowest concentration of the two tested antifoulings, however, there was a suppression of algal growth by increasing the concentration of the two antifoulings but with different degrees. There was a clear inhibition of protein and carbohydrate production by increasing the concentration of the two tested antifoulings. Also, Irgarol 1051 showed a toxic effect higher than Copper, which is one of the essential micronutrients in the marine ecosystem. [ABSTRACT FROM AUTHOR]

Highlights • Changes in growth, photosynthetic activity, and metabolomic profiles induced by artificially stresses were evaluated in eelgrass. • Decreased levels of sugar and increased levels of amino acids in a herbicide-exposed and insufficient light groups are distinctive. • Autophagy is possibly involved in changes in the metabolomic profiles. Abstract This study aimed to elucidate the biological responses of eelgrass (Zostera marina) to artificially induced stresses such as herbicide (Irgarol 1051, Irg) exposure, insufficient light, and high water temperature (27 ± 1.0 °C) by evaluating growth inhibition, photosynthetic activity, and metabolomic profiles. After 14 days, all treatments inhibited growth, but photosynthetic activity was only reduced in the Irg-exposed group. In the Irg-exposed and insufficient light groups, the metabolomic profiles were characterized by decreased levels of sugar (sucrose) and increased levels of amino acids such as glutamine, glycine, and leucine. Biochemical and ultrastructural analyses revealed that the loss of sugar-derived metabolic energy was compensated for by energy generated during autophagic protein degradation. Furthermore, the level of myo-inositol, which has various biological roles and participates in several cellular processes such as cell wall synthesis, stress response, and mineral nutrient storage, was markedly increased in the Irg-exposed and insufficient light groups. A combination of metabolomic analysis with other analyses such as measurement of photosynthetic activity might further elucidate the response of eelgrass to ambient stresses in the natural environment. [ABSTRACT FROM AUTHOR]

An interferometric nanobiosensor for the specific and label-free detection of the pollutant Irgarol 1051 directly in seawater has been settled. Due to the low molecular weight of Irgarol pollutant and its expected low concentration in seawater, the sensor is based on a competitive inhibition immunoassay. Parameters as surface biofunctionalization, concentration of the selective antibody and regeneration conditions have been carefully evaluated. The optimized immunosensor shows a limit of detection of only 3 ng/L, well below the 16 ng/L set by the EU as the maximum allowable concentration in seawater. It can properly operate during 30 assay-regeneration cycles using the same sensor biosurface and with a time-to-result of only 20 min for each cycle. Moreover, the interferometric nanosensor is able to directly detect low concentrations of Irgarol 1051 in seawater without requiring sample pre-treatments and without showing any background signal due to sea matrix effect. [ABSTRACT FROM AUTHOR]

Ship groundings and ice-breakers can cause pollution of the polar environment with antifouling biocides such as diuron and Irgarol 1051. The present study used pulse amplitude modulated fluorometry to compare single and joint toxicities of diuron and Irgarol 1051 on two freshwater taxa of microalgae ( Chlorella and Chlamydomonas ) originating from Arctic and temperate regions. 30 min acute toxicity tests using chlorophyll a (Chl a ) fluorescence revealed that Arctic strains of microalgae were more sensitive to herbicides than their temperate counterparts. Diuron and Irgarol 1051 had equal toxicities in the Arctic species, while Irgarol 1051 was more toxic (EC 50 = 5.55–14.70 μg L −1 ) than diuron (EC 50 = 12.90–>40 μg L −1 ) in the temperate species. Toxicity assessment of various mixtures of diuron and Irgarol 1051 revealed antagonistic, additive, and synergistic effects. Our data suggest that herbicides can adversely affect photosynthesis in Arctic microalgae at relatively low levels, and their impact can increase under complex mixture conditions. [ABSTRACT FROM AUTHOR]

Accumulation of Ot alternative antifoulants in sediment is the focus of this research. Much research had been done on surface sediment, but in this report, the accumulation in the sediment core was studied. The Ot alternative antifoulants, Diuron, Sea-Nine211, and Irgarol 1051, and the latter's degradation product, M1, were investigated in five samples from the northern part of Hiroshima Bay. Ot compounds (tributyltin (TBT) and triphenyltin (TPT)) were also investigated for comparison. In addition, metal (Pb, Cu, Zn, Fe and Mn) levels and chronology were measured to better understand what happens after accumulation on the sea floor. It was discovered that Ot alternative antifoulant accumulation characteristics in sediment were like Ot compounds, with the concentration in the sediment core being much higher than surface sediment. The concentration in sediment seems to have been affected by the regulation of Ot compounds in 1990, due to the concentration of Ot alternative antifoulants and Ot compounds at the survey point in front of the dock, showing an increase from almost the same layer after the regulation. [ABSTRACT FROM AUTHOR]

Abstract: Cyanobacteria are prokaryotic algae found in oceans and freshwaters worldwide. These organisms are important primary producers in aquatic ecosystems because they can provide essential food for grazers and herbivores. In this study, the physiological and biochemical responses of the freshwater cyanobacterium Synechococcus sp. PCC7942 to two organic booster biocides Irgarol 1051 and diuron were compared and evaluated using 96h growth tests in a batch-culture system. The 96h median effective concentrations (EC50) were 0.019 and 0.097μmolL−1 for Irgarol 1051 and diuron, respectively, which indicate that Irgarol 1051 is about 5 times more toxic than diuron to cyanobacteria. Moreover, remarkable physiological and biochemical responses occurred in the Irgarol 1051 and diuron treatments. Irgarol 1051 and diuron stimulated cyanobacterial growth, increased the soluble protein content, and enhanced the catalase (CAT) activity at low concentrations, but inhibited them at high concentrations. However, the malondialdehyde (MDA) and polysaccharide content of the cyanobacteria were only significantly affected by Irgarol 1051. These observations suggest that Irgarol 1051 and diuron are toxic to Synechococcus sp. PCC7942, and their use should be restricted in maritime industries. [Copyright &y& Elsevier]

Abstract: After the widespread ban of TBT, due to its severe impact on coastal biocoenoses, mainly related to its immunosuppressive effects on both invertebrates and vertebrates, alternative biocides such as Cu(I) salts and the triazine Irgarol 1051, the latter previously used in agriculture as a herbicide, have been massively introduced in combined formulations for antifouling paints against a wide spectrum of fouling organisms. Using short-term (60min) haemocyte cultures of the colonial ascidian Botryllus schlosseri exposed to various sublethal concentrations of copper(I) chloride (LC50 =281μM, i.e., 17.8mgCuL−1) and Irgarol 1051 (LC50 >500μM, i.e., >127mgL−1), we evaluated their immunotoxic effects through a series of cytochemical assays previously used for organotin compounds. Both compounds can induce dose-dependent immunosuppression, acting on different cellular targets and altering many activities of immunocytes but, unlike TBT, did not have significant effects on cell morphology. Generally, Cu(I) appeared to be more toxic than Irgarol 1051: it significantly (p <0.05) inhibited yeast phagocytosis at 0.1μM (∼10μgL−1), and affected calcium homeostasis and mitochondrial cytochrome-c oxidase activity at 0.01μM (∼1μgL−1). Both substances were able to change membrane permeability, induce apoptosis from concentrations of 0.1μM (∼10μgL−1) and 200μM (∼50mgL−1) for Cu(I) and Irgarol 1051, respectively, and alter the activity of hydrolases. Both Cu(I) and Irgarol 1051 inhibited the activity of phenoloxidase, but did not show any interactive effect when co-present in the exposure medium, suggesting different mechanisms of action. [Copyright &y& Elsevier]

Booster biocides are organic compounds that are added to antifouling copper-based paints to improve their efficacy. Due to their widespread use, they are common pollutants of marine ecosystems. Some of these compounds show acute and chronic toxic effects in non-targeted organisms at concentrations as low as ng L. The determination of these compounds is therefore important, and for some, which are prioritized in the EU water framework directive, a necessity. Because of their low concentrations and the matrix effect, these contaminants often require a suitable sample preparation step (extraction/pre-concentration) prior to chromatographic determination. The aim of the present article is to review extraction and chromatographic methodologies related to the determination of common booster biocides in marine samples published in the scientific literature. These methodologies include liquid-liquid extraction (LLE), solid phase extraction (SPE), solid phase microextraction (SPME), single drop microextraction (SDME), Soxhlet extraction, microwave-assisted extraction (MAE), supercritical fluid extraction (SFE) and pressurized liquid extraction (PLE) as extraction methods, and both gas and liquid chromatography as determination techniques. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

Abstract: A new sample treatment method for the determination of four common booster biocides (Diuron, TCMTB, Irgarol 1051 and Dichlofluanid) in harbour sediment samples has been developed that uses liquid chromatography–tandem mass spectrometry (LC–MS/MS) after microwave-assisted extraction, followed by clean-up and a solid phase extraction preconcentration step (MAE–SPE). The effects of different variables on MAE–SPE were studied. The recoveries obtained were greater than 75%, and the relative standard deviation was less than 7%. The detection limits ranged between 0.1 and 0.3ngg−1. The developed methodology was successfully applied to the evaluation of the presence of booster biocides in sediment samples from different harbours and marinas of Gran Canaria Island (Canary Islands, Spain). [ABSTRACT FROM AUTHOR]

In this work the risk posed to seawater organisms, predators and humans is assessed, as a consequence of exposure to 12 organic micro-pollutants, namely metronidazole, trimethoprim, erythromycin, simazine, flumequine, carbaryl, atrazine, diuron, terbutryn, irgarol, diphenyl sulphone (DPS) and 2-thiocyanomethylthiobenzothiazole (TCMTB). The risk assessment study is based on a 1-year monitoring study at a Spanish marine fish farm, involving passive sampling techniques. The results showed that the risk threshold for irgarol concerning seawater organisms is exceeded. On the other hand, the risk to predators and especially humans through consumption of fish is very low, due to the low bioconcentration potential of the substances assessed. [Copyright &y& Elsevier]

Abstract: To investigate the deteriorating health of coral reefs in Okinawa, Japan, natural sediment samples were analyzed for diuron, Irgarol 1051, chlorpyrifos, and bisphenol A (BPA) which are hazardous to corals. Samples were analyzed by solid-phase extraction (SPE) followed by high-performance liquid chromatography with tandem mass spectrometry (LC–MS–MS). Although diuron and chlorpyrifos usage is only well recorded for farms and not for cities, these chemicals were detected in both rural and urban areas. Additionally, diuron concentration in urban areas was in some cases higher than in rural areas, which might be caused by greater consumption of these chemicals in home gardens in city areas. Irgarol 1051 was detected in downstream river areas, which are situated far from the source sites such as pier or fishery harbor (0.6–3.2km). This result suggested that Irgarol 1051 could be transported from the river mouths to the sampling sites during flood tides. High BPA concentrations were associated with urban areas (<1.2–22.0μgkg−1), while low concentrations were associated with rural areas (nd–6.8μgkg−1). The river sediments under study are delivered to coral reefs in large quantity through runoff caused by typhoons and other heavy rains. The highly hazardous chemicals are carried into coral reefs on these sediments. Therefore, these hazardous chemical substances may already be influencing the coral reefs. [Copyright &y& Elsevier]

Abstract: Single and joint effects of two antifouling booster biocides, irgarol 1051 (2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine) and diuron (1-(3,4 dichlorophenyl)-3,3 dimethyl urea), their metabolites, M1 (2-methylthio-4-tert-butylamino-s-triazine), DCPMU (1-(3,4-dichlorophenyl)-3 methyl urea), DCPU (1-(3,4 dichlorophenyl urea) and DCA (3,4-dichloroaniline), respectively, as well as copper were examined. Two phytoplanktonic microorganisms, the green alga Dunaliella tertiolecta and the diatom Navicula forcipata were exposed to various concentrations of the aforementioned compounds both alone and in binary mixtures during a period of 96h. Estimation of EC50 values was performed by daily cell number counting of the tested microorganisms. The toxicity of the six compounds and the metal, applied singly, was found to be, in decreasing order, irgarol 1051>diuron>M1>DCPMU>DCA>Cu>DCPU and irgarol 1051>diuron>M1>DCA for the green alga and the diatom, respectively. Diatoms were found to be more sensitive in the presence of all the tested compounds, except diuron. Co-existence of irgarol 1051 and M1 revealed additive effects on both microorganisms. Same results were observed owing to the joint action of copper with either irgarol 1051 or M1 for almost all the examined mixtures. Combined effects of diuron with its metabolites DCPMU and DCA resulted in synergism in almost all cases, for both species of phytoplankton. On the contrary, antagonistic effects were observed owing to the joint action of copper with either diuron or one of its metabolites. [Copyright &y& Elsevier]

The effect of resuspending sediment contaminated with Irgarol 1051 based antifouling paint particles on the green macroalga Ulva intestinalis was examined. U. intestinalis was also exposed to sediment spiked with Irgarol 1051. The macroalga were exposed over 21 days to the resuspension of sediments containing 61.2mgkg−1 of antifouling paint particles containing Irgarol 1051 that provided aqueous Irgarol 1051 concentrations of approximately 0.3μgl−1, Irgarol 1051 and appropriate controls. The growth response was compared with that for ‘clean’ sediment. Resuspension of sediment was associated with reduced growth when compared to seawater alone. Resuspension of sediment spiked with Irgarol 1051 was associated with a greater reduction in growth, with growth being significantly reduced when sediment containing antifouling paint particles was resuspended. The data suggest that the prolonged disturbance of sediments containing antifouling paint particles in marinas represents a potential and as yet unquantified hazard to photosynthetic organisms. [Copyright &y& Elsevier]

Abstract: Two major antifouling biocides used worldwide, Irgarol 1051 and diuron, and their degradation products in Shoreham Harbour and Brighton Marina, UK were studied during 2003–2004. The highest concentrations of Irgarol 1051 were 136 and 102 ng L−1 in water and 40 and 49 ng g−1 dry weight in sediments for Shoreham Harbour and Brighton Marina, respectively. As the degradation product of Irgarol 1051, M1 was also widespread, with the highest concentration of 59 ng L−1 in water and 23 ng g−1 in sediments in Shoreham Harbour, and 37 ng L−1 in water and 5.6 ng g−1 in sediments in Brighton Marina. The target compounds showed enhanced concentrations during the boating season (May–July), when boats were being re-painted (January–February), and where the density of pleasure crafts was high. Overall, the concentration of Irgarol 1051 decreased significantly from late 2000 to early 2004, indicating the effectiveness of controlling its concentrations in the marine environment following restricted use. Diuron was only detected in 14% of water samples, and mostly absent from sediment samples. [Copyright &y& Elsevier]

Abstract: Antifouling paints are used to reduce the attachment of living organisms to the submerged surfaces of ships, boats and aquatic structures, usually by the release of a biocide. Two ‘booster’ biocides in common use are the triazine herbicide Irgarol 1051 (N-2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine), and diuron (1-(3,4-dichlorophenyl)-3,3-dimethylurea), which are designed to inhibit algal photosynthesis. Previous research has been directed at the effects of these compounds in marine and estuarine environments. In 2001 we sampled the main rivers and shallow freshwater lakes (Broads) of East Anglia UK for Irgarol 1051, its metabolite GS26575 (2-methylamino-4-tert-butylamino-6-amino-s-triazine) and diuron in order to establish the baseline environmental concentrations of these compounds in freshwater systems of eastern UK and to investigate their possible effects on aquatic plants. Irgarol 1051, GS26575 and diuron were found in water samples collected from 21 locations. The highest concentrations were found in the Norfolk and Suffolk Broads in May. The rivers Great Ouse, Wissey, Bure and Yare also contained all three compounds, as did the Great Ouse Cut-off Channel. The toxicity of these biocides to three macrophyte species (Apium nodiflorum, Chara vulgaris, and Myriophyllum spicatum) was investigated. Deleterious effects on relative growth rate, the maximum quantum efficiency (Fv/Fm) of photosystem II and, for Apium, root mass production were found. C. vulgaris was generally most sensitive; growth, especially of roots, was strongly affected in A. nodiflorum; growth rate of M. spicatum was sensitive to diuron. No observed effect concentrations (NOEC) were interpolated using standard toxicological analysis. These were compared with measured environmental concentrations (MEC) to determine the ranges of risk quotients (MEC/NOEC). Both Irgarol 1051 and diuron represented significant risks to A. nodiflorum and C. vulgaris in this area. [Copyright &y& Elsevier]

A polyclonal antiserum to Irgarol 1051 was developed in sheep and used to construct an enzyme immunoassay method for the measurement of the antifouling compound in river and seawater samples. The antiserum was generated by a hapten derivative, 2-(tert-butylamino)-4-(cyclopropylamino)-6-(thiopropionic acid)-1,3,5-triazine, coupled to a mixture of keyhole limpet hemocyanin and bovine serum albumin, and the competitive enzyme immunoassay was constructed using a plate-coating antigen made of a heterologous new hapten derivative, 2-(tert-butylamino)-4-(cyclopropylamino)-6-(phenoxybenzoic acid)-1,3,5-triazine, linked to gelatine. The assay showed a sensitivity of about 5 ng L-1 in river and seawater matrices with reasonable specificity with respect to commonly used triazines such as atrazine (3%), simazine (>0.1%) and desethylatrazine (>0.01%). However, high cross-reactivity levels were found with ametryn (56%) and prometryn (60%). Tests on the effects of organic solvents on assay performance indicated a high tolerance to methanol but much less so to acetonitrile. The assay was found to be highly reproducible and robust owing to the stability of the sheep antibody and the highly optimised competitive assay reagents which included the use of the new triazine-O-phenoxybenzoic acid derivative. [ABSTRACT FROM AUTHOR]

Tides and freshwater inflow which influence water movement in estuarine areas govern the exposure-regime of pollutants. In this experiment, we examined the in situ impact of double pulses of copper and the herbicide Irgarol 1051 on the photosynthesis of the seagrass, Zostera capricorni. Despite a 4-day recovery period between the two 10 h pulses of toxicant, the effective quantum yield of photosystem II (ΔF/Fm′) and total chlorophyll concentrations indicated that multiple-pulses had a greater impact than a single pulse. During the first exposure period, samples exposed to Irgarol 1051 had ΔF/Fm′ values as low as zero while controls remained around 0.6 relative units. After the second exposure period, treated samples recovered to only 0.4 relative units. Samples exposed to copper had ΔF/Fm′ values around 0.3 relative units during the first exposure period and while these samples recovered before the second dose, they remained below 0.2 relative units after the second exposure period.Alternate samples were also exposed to one toxicant, allowed to recover and then exposed to the other toxicant. ΔF/Fm′ values indicated that copper exposure followed by Irgarol 1051 exposure was more toxic than Irgarol 1051 exposure followed by copper exposure. [Copyright &y& Elsevier]

Irgarol 1051 (2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine), a derivative of s-triazine herbicide, is an antifouling compound used as an alternative to organotins. The compound is highly persistent and is known to be biodegraded only by the white rot fungus, Phanerochaete chrysosporium. We used partially purified manganese peroxidase (MnP) prepared from P. chrysosporium to evaluate its capacity to degrade Irgarol 1051. MnP degraded Irgarol 1051 to two major products, one identified as M1 (identical to GS26575, 2-methylthio-4-tert-butylamino-6-amino-s-triazine) and the other not identified but with same mass spectrum as M1 and a different ultraviolet spectrum. This report clearly demonstrates that this ligninolytic enzyme is involved in the degradation of Irgarol 1051. [Copyright &y& Elsevier]

In 1989, the EU restricted the use of tributyl-tin (TBT) and the International Maritime Organisation (IMO) decided for a world-wide ban on TBT in 2003. As a replacement for TBT, new antifouling agents are entering the market. Environmental risk limits (ERLs) are derived for substances that are used as TBT-substitutes, i.e. the compounds Irgarol 1051, dichlofluanid, ziram, chlorothalonil and TCMTB. ERLs represent the potential risk of the substances to the ecosystem and are derived using data on (eco)toxicology and environmental chemistry. Only toxicity studies with endpoints related to population dynamics are taken into account.For Irgarol 1051 especially plants appear to be sensitive; the mode of action is inhibition of photosynthetic electron transport. Despite the higher sensitivity of the plants, the calculated ERL for water based on plants only is higher than the ERL based on all data due to the lower variability in the plant only dataset. Because there is a mechanistic basis to state that plants are the most sensitive species, we propose to base the ERL for water on the plants only dataset. As dichlofluanid is highly unstable in the water phase, it is recommended to base the ERL on the metabolites formed and not on the parent compound.No toxicity data of the studied compounds for organisms living in sediments were found, the ERLs for sediment are derived with help of the equilibrium partitioning method. For dichlofluanid and chlorothalonil the ERL for soil is directly based on terrestrial data, for Irgarol 1051 and ziram the ERL for soil is derived using equilibrium partitioning.Except for Irgarol 1051, no information was encountered in the open literature on the environmental occurrence in The Netherlands of the chemicals studied. The measured concentrations for Irgarol 1051 are close to the derived ERL. For this compound it is concluded that the species composition and thereby ecosystem functioning cannot be considered as protected. [Copyright &y& Elsevier]

Organic booster biocides were recently introduced as alternatives to organotin compounds in antifouling products, after restrictions imposed on the use of tributyltin in 1987. In this study, the concentrations of three biocides commonly used as antifoulants, Irgarol 1051 (2-methylthio-4-tertiary-butylamino-6-cyclopropylamino-s-triazine), dichlofluanid (N-dichlorofluoromethylthio-N′,N′-dimethyl-N-phenyl sulphamide) and chlorothalonil (2,4,5,6-tetrachloro isophthalonitrile) were determined in sediments from ports and marinas of Greece. Piraeus (Central port, Mikrolimano and Pasalimani marinas), Thessaloniki (Central port and marina), Patras (Central port and marina), Elefsina, Igoumenitsa, Aktio and Chalkida marinas were chosen as representative study sites for comparison with previous monitoring surveys of biocides in coastal sediments from other European countries.Samples were collected at the end of one boating season (October 1999), as well before and during the 2000 boating season. All the compounds monitored were detected at most of sites and seasonal dependence of biocide concentrations were found, with maxima during the period June–September, while the winter period (December–February) lower values were encountered. The concentrations levels ranged from 3 to 690 ng/g dw (dry weight). Highest levels of the biocides were found in marinas (690, 195 and 165 ng/g dw, for Irgarol, dichlofluanid and chlorothalonil respectively) while in ports lower concentrations were observed. Antifouling paints are implicated as the likely sources of biocides since agricultural applications possibly contributed for chlorothalonil and dichlofluanid inputs in a few sampling sites. [Copyright &y& Elsevier]

The photochemical degradation of irgarol 1051 has been studied in different natural waters (sea, river, lake) as well as in distilled water under natural and simulated solar irradiation. The effect of dissolved organic matter (DOM) such as humic and fulvic substances on the photodegradation rate was also studied under simulated sunlight. The addition of DOM in distilled water was shown to greatly increase the rate of degradation, however, a decrease was observed in natural waters. The photodegradation proceeds via pseudo-first-order reaction in all cases with half-lives ranged from 2 to 1432 h. In natural and humic water irgarol 1051 photodegradation gave rise to the dealkylated derivative demonstrating that the transformation of irgarol 1051 depend on the constitution of the irradiated media and especially from DOM concentration and type. The byproducts identified by GC–MS techniques were: 2-methylsulfonyl-4-terbutylamino-6-cyclopropylamino-s-triazine, 2-hydroxy-4-terbutylamino-6-cyclopropylamino-s-triazine, 2-methylthio-4-terbutylamino-6-ethylamino-s-triazine, 2-methylsulfonyl-4-terbutylamino-6-amino-s-triazine and diaminohydroxy-s-triazine. [Copyright &y& Elsevier]

Irgarol 1051 is highly toxic to marine autotrophs and has been widely used as an antifouling booster biocide. This study tested the toxicities of two s -triazine derivatives of Irgarol, namely M2 (3-[4- tert -butylamino-6-methylthiol- s -triazin-2-ylamino]propionaldehyde) and M3 (2-methylthio-4,6-bis- tert -butylamino- s -triazine) to two marine diatom species, Skeletonema costatum and Thalassiosira pseudonana through standard acute (96h) and chronic (7d) growth inhibition tests. Results showed that both of the two chemicals significantly inhibited the growth of S. costatum (M2: 96h-EC50 = 6789.7 μg L−1, 7d-EC50 = 3503.7 μg L−1; M3: 96h-EC50 = 45193.9 μg L−1, 7d-EC50 = 5330.0 μg L−1) and T. pseudonana (M2: 96h-EC50 = 366.2 μg L−1, 7d-EC50 = 312.5 μg L−1; M3: 96h-EC50 = 2633.4 μg L−1, 7d-EC50 = 710.5 μg L−1), while their toxicity effects were much milder than Irgarol and its major degradation product M1. By comparing with previous findings, the susceptibilities of these s -triazine compounds to two tested species were ranked as: Irgarol > M1 ≫ M2 > M3. This study promotes future research efforts on better understanding of the ecotoxicities of M2 and M3, and incorporating such information to improve the current monitoring, risk assessment and regulation of the use of Irgarol. Image 1 • Toxicities of two Irgarol derivatives M2 and M3 to two marine diatoms were tested. • Both M2 and M3 significantly inhibited the growth of two diatom species. • Thalassiosira pseudonana appeared to be more sensitive than Skeletonema costatum. • Toxicity order of Irgarol and its derivatives was: Irgarol > M1 ≫ M2 > M3. [ABSTRACT FROM AUTHOR]

Antifoulant Irgarol 1051 (2-methythiol-4-tert-butylamino-6-cyclopropylamino-s-triazine) can be photodegraded into M1 (2-methylthio-4-tert-butylamino-6-amino-s-triazine) and M2 (3-4-tert-butylamino-6-methylthiol-s-triazin-2-ylamino]propion-aldehyde). M3 (2-methylthio-4,6-bis-tert-butylamino-s-triazine) was also detected as a side-product in Irgarol. This study aimed to investigate the combined toxicity of a mixture of these s-triazine compounds to eight marine organisms. A degraded mixture of Irgarol in artificial seawater was obtained by photolysis over 42 d and its composition was quantified by HPLC-UV analyses. Based on short-term toxicity tests on eight selected marine species, the mixture posed significant phytotoxic effects to the cyanobacteria (Chroococcus minor and Synechococcus sp.), the diatoms (Skeletonema costatum and Thalassiosira pseudonana), the macroalgae (Ulva lactuca and Caulerpa peltata) and the dinoflagellate (Prorocentrum dentatum), though the mixture was less toxic to the copepod Tigriopus japonicus. Both Independent Action and Concentration Addition models can generate reasonably satisfactory predictions on the overall mixture toxicity to the two diatoms, implying that the four compounds likely share a similar mode of action and resemble an additive effect in the mixture., (Copyright © 2019 Elsevier Ltd. All rights reserved.)