Development and Application of a Novel QuEChERS Method for Monitoring of Tributyltin and Triphenyltin in Bottom Sediments of the Odra River Estuary, North Westernmost Part of Poland.

A Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) extraction method combined with Liquid Chromatography-Tandem Mass Spectrometry (LC-MS/MS) for determination of organotin compounds (OTC) has been newly developed. The novel analytical method was validated and the quality of the results was tested by the use of certificate reference material of freshwater sediment BCR 646. The method was applied in determination of OTC concentration in real samples of bottom sediments collected from the Polish part of Odra River Estuary. The samples came from locations with different anthropogenic impact. Additionally, the extraction recovery of OTC and matrix effect on MS signal response was investigated based on those real environmental samples. It was found that organic compounds and anthropogenic contaminations present in bottom sediments may affect extraction efficiency of the organotin compounds (OTC) and change the matrix effect on MS signal response. The highest concentrations of tributyltin were found in bottom sediments collected from locations in vicinity of the Szczecin harbor and shipyards. The presence of triphenyltin above limit of detection (5 ng TPhT/g of sediment) was observed only in two samples and its concentration was several times lower compared to concentration of tributyltin (from 58 ng/g to 5263 ng/g). In spite of the fact that, the application of TBT-based paints on hull of vessel entering EU ports has been banned by European Commission regulation No. 782/2003 since 2008, the OTC compounds are still present in bottom sediment and pose significant threat to the environment. This threat should be taken into account during dredging of waterways and other hydrotechnical works.

[Determination of Tributyltin and Triphenyltin in Fish and Shellfish Using Accelerated Solvent Extraction and Liquid Chromatography with Tandem Mass Spectrometry].

A determination method for tributyltin (TBT) and triphenyltin (TPT) in fish and shellfish using an accelerated solvent extractor (ASE) and LC-MS/MS was developed. The chromatographic separation was conducted on a Poroshell 120 EC-C18 column using an isocratic mobile phase of 0.1% formic acid in 70% methanol. Sample preparation was performed using ASE at 125℃ with n-hexane and a cleanup using a Florisil cartridge. Internal calibration curves using deuterium-labeled TBT and TPT were employed for quantification. For both TBT and TPT, the calibration curves were linear in the range of 0.2-250 ng/mL, and the method quantification limits were 0.8 ng/g for both TBT and TPT. A National Institute for Environmental Studies certified reference material, No. 15 (adductor muscle of scallop), was analyzed to assess the performance of the developed method. The trueness, relative standard deviations of repeatability, and within laboratory reproducibility of this method, evaluated using a recovery test with four spiked fish species and one shellfish, ranged from 89.3 to 105.3%, 1.0 to 4.5%, and 1.3 to 7.6%, respectively.

On the effectiveness of tributyltin ban: Distribution and changes in butyltin concentrations over a 9-year period in Klaipeda Port, Lithuania.

This study provides an insight on a long-term butyltin pressure, spatio-temporal changes and current tributyltin distribution in the Klaipeda Port sediments. Moreover, it examines whether the restrictions on tributyltin use led to a decreased pollution in the area. Changes over a 9-year period in tributyltin and its metabolites concentrations were analyzed in surface sediments from semi-enclosed bays of the Port. Reduction in organotin level was observed after tributyltin ban came into force: tributyltin concentration reached 3000 ng Sn g-1 d.w. in 2005 whereas 1793 ng Sng-1 d.w. was found to be the highest tributyltin concentration in 2013. The highest contamination was detected in the zones with ship maintenance activity. As late as in 2013, the latter areas still exhibited fresh tributyltin input while the progress of organotin degradation has been observed for other sampling stations along the Port.

Preliminary studies about the role of physicochemical parameters on the organotin compound dynamic in a South American estuary (Bahía Blanca, Argentina).

This work provides a preliminary study of the destination, mobility, and availability of tributyltin (TBT), dibutyltin (DBT), and monobutyltin (MBT) in contaminated sediments and water column within Puerto Rosales Port, located in the middle zone of the Bahía Blanca Estuary (Argentina). Therefore, this study presents the first comprehensive results of the role of several physicochemical parameters (temperature, pH, Eh, salinity, turbidity, organic matter, chlorophyll, and macronutrients) in behavior of organotin compounds (OTCs) in a marine-coastal ecosystem. The samples were collected seasonally in May, August, and November during 2014. Levels of OTCs were determined in sediments and water column samples by means of gas chromatography-mass spectrometry analysis. Degradation index analyses suggested not recent inputs of TBT at the area of study. However, results submitted a continuous input of TBT into the column water; further, its distribution and degradation pattern were shown to be influenced by salinity, turbidity, particulate organic matter, chlorophyll, and nitrates. These last two parameters, chlorophyll and nitrates, also were very important for sediment samples. Chlorophyll together with high temperatures recorded in the surface sediments triggers biodegradation process of TBT and DBT resulting in high MBT levels while nitrates seemed to promote debutylation process. Furthermore, pH appeared to influence drastically the adsorption/desorption activity of TBT and DBT in sediment. Finally, the Eh obtained suggested a degradation of TBT thanks to the presence of Fe (III) in this compartment. In addition, in fact, the results outlined a possible MBT additional input that contributes to the pollution observed in the study area. Graphical abstract Organotin compounds behavior according to several physicochemical parameters.

Tributyltin: Advancing the Science on Assessing Endocrine Disruption with an Unconventional Endocrine-Disrupting Compound.

Tributyltin (TBT) has been recognized as an endocrine disrupting chemical (EDC) for several decades. However, only in the last decade, was its primary endocrine mechanism of action (MeOA) elucidated-interactions with the nuclear retinoid-X receptor (RXR), peroxisome proliferator-activated receptor γ (PPARγ), and their heterodimers. This molecular initiating event (MIE) alters a range of reproductive, developmental, and metabolic pathways at the organism level. It is noteworthy that a variety of MeOAs have been proposed over the years for the observed endocrine-type effects of TBT; however, convincing data for the MIE was provided only recently and now several researchers have confirmed and refined the information on this MeOA. One of the most important lessons learned from years of research on TBT concerns apparent species sensitivity. Several aspects such as the rates of uptake and elimination, chemical potency, and metabolic capacity are all important for identifying the most sensitive species for a given chemical, including EDCs. For TBT, much of this was discovered by trial and error, hence important relationships and important sensitive taxa were not identified until several decades after its introduction to the environment. As recognized for many years, TBT-induced responses are known to occur at very low concentrations for molluscs, a fact that has more recently also been observed in fish species. This review explores the MeOA and effects of TBT in different species (aquatic molluscs and other invertebrates, fish, amphibians, birds, and mammals) according to the OECD Conceptual Framework for Endocrine Disruptor Testing and Assessment (CFEDTA). The information gathered on biological effects that are relevant for populations of aquatic animals was used to construct Species Sensitivity Distributions (SSDs) based on No Observed Effect Concentrations (NOECs) and Lowest Observed Effect Concentrations (LOECs). Fish appear at the lower end of these distributions, showing that they are as sensitive as molluscs, and for some species, even more sensitive. Concentrations in the range of 1 ng/L for water exposure (10 ng/g for whole-body burden) have been shown to elicit endocrine-type responses, whereas mortality occurs at water concentrations ten times higher. Current screening and assessment methodologies as compiled in the OECD CFEDTA are able to identify TBT as a potent endocrine disruptor with a high environmental risk for the original use pattern. If those approaches had been available when TBT was introduced to the market, it is likely that its use would have been regulated sooner, thus avoiding the detrimental effects on marine gastropod populations and communities as documented over several decades.

Imposex in Nassarius nitidus (Jeffreys, 1867) as a possible investigative tool to monitor butyltin contamination according to the Water Framework Directive: A case study in the Venice Lagoon (Italy).

Butyltin (TBT, DBT, and MBT) effects on molluscs, especially endocrine disruption in bivalves and gastropods, have been widely investigated. Imposex, the superimposition of male characters onto female gonochoristic Caenogastropods, is the most studied biological effect of TBT. TBT compounds are among the priority hazardous substances within Directives 2000/60/EC (WFD) and 2008/105/EC. The Environmental Quality Standards (EQSs) set by the WFD for TBT are quite difficult to quantify by means of chemical analysis, without the use of expensive and high performance methods. Assuming that EQSs set for TBT were derived from evidence of imposex development at very low concentrations, this specific biomarker could be used as an indirect measure of assessing levels of bioavailable BTs. Therefore, this study aims to validate the use of imposex development as an investigative tool to monitor the bioavailable fraction of BTs within the WFD, by comparing imposex levels and BT concentrations in Nassarius nitidus from the Venice Lagoon. BT concentrations and imposex levels in N. nitidus, collected in 2013, had decreased when compared to previous studies in the same area. Both VDSI and RPLI correlated positively with BT body burden in females, confirming that imposex is a valid tool to monitor bioavailable BTs. However, TBT is still a matter of concern in the Venice Lagoon, as TBT concentrations were still higher than its degradation products suggesting recent fresh TBT inputs in the studied area. To propose imposex levels as an indicator of the impact of BTs within the WFD, classification class boundaries and Ecological Quality Ratios were introduced. As a preliminary attempt, imposex levels were also compared to the OSPAR Commission EcoQOs which linked imposex levels in Nassarius reticulatus with TBT concentrations in water. Based on this comparison the degree of imposex development in the Venice Lagoon suggested that TBT concentrations in water should be over the EQS-AA concentration and, at one site, also over the EQS-MAC. From all the results obtained in this work, it appears that imposex evaluation in N. reticulatus could give information about the ecological status regarding BT compounds under the WFD and also be used to monitor their effects and support chemical analyses until more sensitive methods become available.

Microbes a Tool for the Remediation of Organotin Pollution Determined by Static Headspace Gas Chromatography-Mass Spectrometry.

Tributyltin (TBT) is one of the most toxic anthropogenic compounds introduced into the marine environment. Despite its global ban in 2008, TBT is still a problem of great concern due to its high affinity for particulate matter, providing a direct and potentially persistent route of entry into benthic sediments. Bioremediation strategies may constitute an alternative approach to conventional physicochemical methods, benefiting from the microorganism's potential to metabolize anthropogenic compounds. In this work, a simple, precise and accurate static headspace gas chromatography method was developed to investigate the ability of TBT degrading microbes in sedimentary microcosms over a period of 120 days. The proposed method was validated for linearity, repeatability, accuracy, specificity, limit of detection and limit of quantification. The method was subsequently successfully applied for the detection and quantification of TBT and degradation compounds in sediment samples on day 0, 30, 60, 90 and 120 of the experiment employing the principles of green chemistry. On day 120 the concentration of TBT remaining in the microcosms ranged between 91.91 ng/g wet wt for the least effective microbial inoculant to 52.73 ng/g wet wt for the most effective microbial inoculant from a starting concentration of 100 ng/g wet wt.

Effects of harbor activities on sediment quality in a semi-arid region in Brazil.

Tropical marine environments are rich in biodiversity and the presence of harbor activities in these areas can harm the coastal ecosystems. In this study, we assessed sediment quality of two harbors from a tropical region in Brazil by applying multiple lines-of-evidence approach. This approach included the integration of results on: (1) grain size, organic matter, organic carbon, nitrogen, phosphorus, trace metals, polycyclic aromatic hydrocarbons, linear alkylbenzenes, and tributyltin; (2) acute toxicity of whole sediments and chronic toxicity of liquid phases; and (3) benthic community descriptors. Our results revealed that the main contaminants detected in sediments from Mucuripe and Pecém Harbors were chromium, copper, nitrogen, zinc, and tributyltin. These toxicants arise from typical harbor activities. However, the changes in benthic composition and structure appear to depend on a combination of physical impacts, such as the deposition of fine sediments and the toxic potential of contaminants, especially in Mucuripe. Thus, apart from toxicants physical processes are important in describing risks. This information may assist in management and conservation of marine coastal areas.

Imposex in Reishia clavigera as an Indicator to Assess Recovery of TBT Pollution After a Total Ban in South Korea.

The temporal changes in the frequency and degree of imposex and tributyltin (TBT) levels in gastropod (Reishia clavigera) were evaluated in Jinhae Bay, 5 and 10 years after the total ban on TBT usage in South Korea. The frequency and degree of imposex decreased significantly after the ban, accompanied by an increase in the female-to-male ratio. The TBT concentrations in R. clavigera also decreased significantly after the ban. There were good correlations between the TBT concentration in rock shell and both the degree of imposex and the female-to-male ratio. The total TBT ban effectively reduced the TBT levels and the frequency and degree of imposex in R. clavigera. However, the current low exposure level in the study area is still sufficient to cause imposex in R. clavigera. More time is needed to reduce the TBT levels to levels that do not have adverse biological effects on R. clavigera.

A temporal and spatial monitoring of organotin pollution in a harborside region of Brazil by imposex and ecological quality ratio using Leucozonia nassa.

This study represents the first use of Leucozonia nassa (Mollusca-Gastropoda) in a program of long-term monitoring. Specimens of L. nassa were collected between 2006 and 2014 and analyzed for the occurrence of imposex in two areas in Southeastern Brazil, one control area and another characterized by the presence of many ports and marinas. Imposex was evaluated in nine sites based on the percentage of females exhibiting imposex (I%), relative penis length index and vas deferens sequence index, classical indices to evaluate tributyltin (TBT) impacts. Moreover, this study uses for the first time in a tropical environment the ecological quality ratio (EQR), an approach to verify the imposex levels as an indicator of the impact by organotin compounds according to the EU Water Framework Directive. The results confirm the occurrence of high levels of imposex in L. nassa with all the indices evaluated. Furthermore, the results also indicate that, despite the international ban, antifouling paints based on TBT are still possibly used in Brazil. In addition, this study shows that L. nassa has the characteristics that make it a suitable bioindicator to monitor TBT pollution, and that the use of the EQR may create important data regarding this problem.

Managing dredged material in the coastal zone of the Baltic Sea.

This article deals with the legal and practical recommendations for the management of dredged material in the riparian countries of the Baltic Sea. The recommendations are contained in three conventions: LC, 2000. London Convention (1972), Convention on the Protection of the Marine Environment of the Baltic Sea area (Helsinki Convention) (1992), the OSPAR Convention (1972). Different approaches to evaluating the contamination level of dredge spoils, used by the Baltic Sea riparian countries, have been characterized. The differences in those approaches manifest themselves by various concentration limits for contaminants, which form a basis for the classification of dredged material as either contaminated or non-contaminated, and thus determine how the spoils will be processed further. Based on the collected information about the concentration limits for contaminants of surface sediments in the coastal ports, it was pointed out that it is necessary to conduct routine monitoring of heavy metals, polycyclic aromatic hydrocarbons, polychlorinated biphenyls, tributyltin, and petroleum hydrocarbons in dredged sediments in all the Baltic Sea states. On the other hand, the monitoring of polychlorinated dibenzo-p-dioxins/furans, organochlorine, and organophosphoric pesticides is only needed in locations that are suspected of historical or being the local contamination sources. Due to significant economic limitations of chemical determinations, it is important to consider a simple screening test of sediment that would say whether sediment may be "contaminated" and qualifies for more detailed and costly chemical research. It may be typical basic physical-chemical analysis of sediments or ecotoxicological classification of sediments.Despite environmentally friendly tendencies, the practical application of dredged material within the Baltic Sea area is very limited. Dredged material is most frequently stored at the specifically designated sites. From among the practical uses of dredge spoils, beach nourishment is of the highest significance.In the conclusion, the new proposed management procedure of dredged material was presented.

Contaminants in Liquid Organic Fertilizers Used for Agriculture in Japan.

To provide an overview of anthropogenic contaminants in liquid organic fertilizers (LOFs), products from four biogas plants in Kyushu, Japan, were analyzed for a wide range of contaminants, including copper, cadmium, tributyltin (TBT), dibutyltin (DBT), perfluorooctane sulfonate, 952 semi-volatile organic compounds, and 89 antibiotics. The highest concentrations of copper (31.1 mg/L) and cadmium (0.08 mg/L) were found in LOFs from the Hita biogas plant. Only ofloxacin and sulfapyridine were detected in total 89 antibiotics screened. TBT, DBT, and perfluorooctane sulfonate were present at low concentrations in the LOFs from all four locations. Among the 952 semi-volatile organic compounds, 78 compounds were detected in at least one sample and were present at concentrations between 1.2 and 139.6 mg/L. On the basis of comparisons with previous studies and quality standards for the use of organic fertilizers, the concentrations of contaminants in the studied LOFs indicate that they might be safe for agricultural purposes.

An assessment of butyltins and metals in sediment cores from the St. Thomas East End Reserves, USVI.

Tributyltin (TBT) concentrations near a marina complex in Benner Bay on St. Thomas, US Virgin Islands, were elevated relative to other areas in a larger study of the southeastern shore of the island. At the request of the USVI Coastal Zone Management Program, sediment cores and surface sediment samples were collected to better define the extent and history of TBT deposition in the vicinity of Benner Bay. The sediment cores were sectioned into 2-cm intervals and dated with 210Pb and 137Cs. The core sections and the surface samples were analyzed for butyltins and 16 elements. Deposition rates varied from 0.07-5.0 mm/year, and were highest in the marina complex. Core ages ranged from 54 to 200 years. The bottoms of the cores contained shell hash, but the top layers all consisted of much finer material. Surface concentrations of TBT exceeded 2000 ng Sn/g (dry weight) at two locations. At a depth of 8 cm TBT exceeded 8800 ng Sn/g in the marina complex sediment. Based on the ratio of tributyltin to total butyltins, it appears that the marina sediments are the source of contamination of the surrounding area. There is evidence that vessels from neighboring islands may also be a source of fresh TBT. Copper concentrations increase over time up to the present. Gradients of virtually all metals and metalloids extended away from the marina complex. NOAA sediment quality guidelines were exceeded for As, Pb, Cu, Zn, and Hg.

Chemical characterisation of dredged sediments in relation to their potential use in civil engineering.

During capital and/or maintenance dredging operations, large amounts of material are produced. Instead of their discharge, dredged sediments may be a valuable natural resource if not contaminated. One of the possible areas of application is civil engineering. In the present work, the environmental status of seaport dredged sediment was evaluated in order to investigate its potential applicability as a secondary raw material. Sediments were analysed for element concentrations in digested samples, aqueous extracts and fractions from sequential extraction; for fluoride, chloride and sulphate concentrations in aqueous extracts; and for tributyltin (TBT). Granulometric and mineralogical compositions were also analysed. The elemental impact was evaluated by calculation of the enrichment factors. The total element concentrations determined showed moderate contamination of the dredged sediments as was confirmed also by their moderate enrichment factors, presumably as a result of industrial and port activities. Elemental concentrations in the aqueous extract were very low and therefore do not represent any hazard for the environment. The water-soluble element concentrations were under the threshold levels set by the EU Directive on the landfill of waste, on the basis of which the applicability of dredged sediments in civil engineering is evaluated, while the content of chloride and sulphate were above the threshold levels. It was found out that due to the large amounts of sediment available, civil engineering applications such as the construction of embankments and backfilling is the most beneficial recycling solution at present.

Adsorption and degradation processes of tributyltin and trimethyltin in landfill leachates treated with iron nanoparticles.

Biotic and abiotic degradation of toxic organotin compounds (OTCs) in landfill leachates is usually not complete. In this work adsorption and degradation processes of tributyltin (TBT) and trimethyltin (TMeT) in leachate sample treated with different iron nanoparticles (FeNPs): Fe(0) (nZVI), FeO and Fe3O4 were investigated to find conditions for their efficient removal. One sample aliquot was kept untreated (pH 8), while to the others (pH 8) FeNPs dispersed with tetramethyl ammonium hydroxide (TMAH) or by mixing were added and samples shaken under aerated conditions for 7 days. The same experiments were done in leachates in which the pH was adjusted to 3 with citric acid. Size distribution of TBT and TMeT between particles >5 µm, 0.45-5 µm, 2.5-0.45 µm, and <2.5 nm was determined by sequential filtration and their concentrations in a given fraction by gas chromatography coupled to inductively coupled plasma mass spectrometry (GC-ICP-MS). Results revealed that most of the TBT or TMeT was present in fractions with particles >2.5 or <2.5 nm, respectively. At pH 8 adsorption of TBT to FeNPs prevailed, while at pH 3, the Fenton reaction provoked degradation of TBT by hydroxyl radicals. TBT was the most effectively removed (96%) when sequential treatment of leachate with nZVI (dispersed by mixing) was applied first at pH 8, followed by nZVI treatment of the aqueous phase, previously acidified to pH 3 with citric acid. Such treatment less effectively removed TMeT (about 40%). It was proven that TMAH provoked methylation of tin, so mixing was recommended for dispersion of nZVI.

Tributyltin chloride (TBTCl)-enhanced exopolysaccharide and siderophore production in an estuarine Alcaligenes faecalis strain.

Tributyltin chloride (TBTCl) has been used extensively as an antifouling agent in ship paints, which results in the contamination of aquatic sites. These contaminated sites serve as enrichment areas for TBTCl-resistant bacterial strains. One TBTCl-resistant bacterial strain was isolated from the sediments of Zuari estuary, Goa, India, which is a major hub of various ship-building activities. Based on biochemical characteristics and 16S rDNA sequence analysis, this bacterial strain was identified as Alcaligenes faecalis and designated as strain SD5. It could degrade ≥3 mM TBTCl by using it as a sole carbon source and transform it into the less toxic dibutyltin chloride, which was confirmed by nuclear magnetic resonance and mass spectroscopy. Interestingly, this bacterial strain also showed enhanced exopolysaccharide and siderophore production when cells were exposed to toxic levels of TBTCl, suggesting their involvement in conferring resistance to this antifouling biocide as well as degradative capability respectively.

Imposex in the dogwhelk (Nucella lapillus): 22-year monitoring around England and Wales.

Six imposex surveys in the dogwhelk (Nucella lapillus) have been conducted over the past two decades to assess legislation effectiveness controlling the use of tri-butyl tin (TBT) by the maritime shipping industry. This study firstly analysed the results of the 2014 survey and secondly carried out a trend assessment of the same 88 sampled sites between 1997 and 2014 of which 65 showed statistically significant reductions. To highlight the magnitude of change, the Vas Deferens Sequence stages (VDS) of the same 56 sites sampled in 1997 and 2010 showed that the Vas Deferens Sequence Index (VDSI) reduced statistically significantly from 2.89 and 0.42, respectively. These data confirm that the legislation enacted, latterly through the International Maritime Organization (IMO) during 2003 to 2008, has been effective in progressively reducing the impact of TBT in the marine environment. Nevertheless, the 2014 results show that two of 18 sampled sites (Gurnard Bay and St. Mawes) are still above the Ecotoxicological Assessment Criteria (EAC) derived for TBT (VDSI ≤ 2).

Biodegradation of Tributyltin (TBT) by Extremophile Bacteria from Atacama Desert and Speciation of Tin By-products.

Biodegradation of tributyltin (TBT) by four tin resistant Gram negative bacteria isolated from extremely contaminated river sediments in the Atacama Desert in Chile was studied. Moraxella osloensis showed the greatest resistance and degradation capability of TBT, producing less toxic by-products, such as dibutyltin (DBT) and inorganic tin. In 7 days, approximately 80 % of TBT degradation was achieved, generating close to 20 % of DBT as degradation product. The degradation rate constant (k) was 0.022 [day(-1)] and TBT half-life (t1/2) in culture was 4.3 days. Debutylation is stated a probable mechanism of TBT degradation.

Determination of tributyltin in marine sediment and waters by pressurised solvent extraction and liquid chromatography-tandem mass spectrometry.

In this study, tributyltin (TBT) was extracted from marine sediment matrix with the use of pressurised solvent extraction (PSE), which uses high-temperature and -pressure conditions to increase extraction efficiency. The analyte was chromatographically resolved using a liquid chromatography-tandem mass spectrometry (LC-MS/MS) system with a pentafluorophenyl (PFP) column and a methanol/aqueous formic acid mobile phase gradient, and was detected by MS/MS as product fragments after collisionally induced dissociation (CID) of the cationic parent molecule. This study represents the first application of PSE extraction combined with LC-MS/MS analysis for the determination of TBT in sediments. The method has been validated according to the International Organisation for Standardisation (ISO) 17025:2001 and affords automated extraction of sediment samples with high-sensitivity analysis. The full method limit of detection was established as 1.25 ng Sn g(-1) with an instrument detection limit of 0.01 ng Sn g(-1). The chromatographic procedure may also be applied for the direct analysis of water matrices without the need for sample manipulation, and therefore represents a combined analytical approach for the monitoring of TBT contamination in marine or estuarine ecosystems.

Concentration of antifouling biocides and metals in sediment core samples in the northern part of Hiroshima Bay.

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.