Applicability of microwave-assisted extraction combined with LC-MS/MS in the evaluation of booster biocide levels in harbour sediments

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 0.3 ng g⁻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).     

Mixture Toxicity of the Antifouling Compound Irgarol to the Marine Phytoplankton Species Dunaliella tertiolecta

This study examined the toxicity of irgarol, individually and in binary mixtures with three other pesticides (the fungicide chlorothalonil, and the herbicides atrazine and 2,4-D), to the marine phytoplankton species Dunaliella tertiolecta. Standard 96-h static algal bioassays were used to determine pesticide effects on population growth rate. Irgarol significantly inhibited D. tertiolecta growth rate at concentrations ≥ 0.27 μ g/L. Irgarol was significantly more toxic to D. tertiolecta than the other pesticides tested (irgarol 96 h EC₅₀ = 0.7 μ g/L; chlorothalonil 96 h EC₅₀ = 64 μ g/L; atrazine 96 h EC₅₀ = 69 μ g/L; 2,4-D 96 h EC₅₀ = 45,000 μ g/L). Irgarol in mixture with chlorothalonil exhibited synergistic toxicity to D. tertiolecta, with the mixture being approximately 1.5 times more toxic than the individual compounds. Irgarol and atrazine, both triazine herbicides, were additive in mixture. The toxicity threshold of 2,4-D was much greater than typical environmental levels and would not be expected to influence irgarol toxicity. Based on these interactions, overlap of certain pesticide applications in the coastal zone may increase the toxicological risk to resident phytoplankton populations.     

上海港区船舶防污漆中Irgarol 1051的环境风险评价

Irgarol 1051是一种常用于船舶防污漆的杀生活性物质。为了评价船舶防污漆杀生活性物质Irgarol 1051的海洋环境风险,根据ISO 13073-1的评价原则和程序,对其进行环境危害评价、环境暴露评价和风险表征。通过对公共数据库的文献检索获取数据,从理化性质、环境行为、生态毒性3个方面评价Irgarol 1051的环境危害。采用评估因子法计算Irgarol 1051的预测无效应浓度(PNEC)。采用质量守恒法计算Irgarol 1051在海水中的释放率,通过MAMPEC v3.0模型推导上海洋山深水港的集装箱船区、码头、航道等暴露场景的预测环境浓度(PEC)。经过比较上述暴露场景的风险商值(PEC/PNEC)发现,港口的海水相风险商值大于1,Irgarol 1051的环境风险需要关注。     

Analytical methods for the determination of 9 antifouling paint booster biocides in estuarine water samples

Analytical procedures for the determination of nine organic booster biocides which are currently licensed for use in marine antifouling paints, and are thought likely to occur at concentrations in the ng 1⁻¹ range in estuarine water samples, are reviewed. A robust multiresidue method for the determination of four compounds (chlorothalonil, dichlofluanid, diuron and Irgarol 1051) is suggested. A route for the development of a method for the analysis of zinc pyrithione is outlined, based on an extraction method and subsequent derivatisation prior to determination by HPLC with fluorescence detection. Methodology for Zineb, Kathon 5287, TCMS pyridine and TCMTB is less clearly defined.     

Distribution of pesticides and bisphenol A in sediments collected from rivers adjacent to coral reefs

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 (0.6–3.2 km). 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 (<1.2–22.0 μg kg⁻¹), while low concentrations were associated with rural areas (nd–6.8 μg kg⁻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.     

Effects of the anti-fouling herbicide Irgarol 1051 on two life stages of the grass shrimp,Palaemonetes pugio

This study investigated lethal and sublethal effects (glutathione, lipid peroxidation, cholesterol, and acetylcholinesterase) of the anti-fouling herbicide Irgarol 1051 on larval and adult grass shrimp (Palaemonetes pugio). The 96-hour LC50 test for larvae resulted in an estimated LC50 of 1.52 mg/L (95% confidence interval [CI] 1.26–1.85 mg/L). The adult 96-h LC50 was 2.46 mg/L (95% CI = 2.07–2.93 mg/L). Glutathione, lipid peroxidation, cholesterol and acetylcholinesterase levels were not significantly affected in adult grass shrimp by exposure of up to 3.00 mg/L irgarol. Lipid peroxidation and acetylcholinesterase levels in the larvae were significantly higher than controls in the highest irgarol exposures of 1.0 and 2.0 mg/L, respectively. Cholesterol levels were significantly reduced in larvae in all four irgarol concentrations tested while glutathione levels were not significantly affected in larvae. Both lethal and sublethal effects associated with irgarol exposure were only observed at concentrations well above those reported in the environment.     

Environmental and human health risk assessment of organic micro-pollutants occurring in a Spanish marine fish farm

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.     

Immunotoxicity in ascidians: antifouling compounds alternative to organotins: III--the case of copper(I) and Irgarol 1051

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 (60 min) haemocyte cultures of the colonial ascidian Botryllus schlosseri exposed to various sublethal concentrations of copper(I) chloride (LC₅₀ = 281 μM, i.e., 17.8 mg Cu L⁻¹) and Irgarol 1051 (LC₅₀ > 500 μM, i.e., >127 mg L⁻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 0.1 μM (∼10 μg L⁻¹), and affected calcium homeostasis and mitochondrial cytochrome-c oxidase activity at 0.01 μM (∼1 μg L⁻¹). Both substances were able to change membrane permeability, induce apoptosis from concentrations of 0.1 μM (∼10 μg L⁻¹) and 200 μM (∼50 mg L⁻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.     

Multidimensional risk analysis of antifouling biocides

In order to improve the orientation about the long-term sustainability of the use of the antifouling biocides tributyltin (TBT), copper, Irgarol® 1051, Sea-Nine? 211 and zinc pyrithione, used for the protection of fouling in sea-going ships, the risks posed to the marine biosphere due to their use are evaluated. The newly presented method of risk analysis uses release rate, spatiotemporal range, bioaccumulation, bioactivity and uncertainty as 5 dimensions of ecotoxicological risk. For each dimension, a scoring procedure is briefly described. The resulting risk profiles of the antifouling biocides show characteristics of the different substances, but also indicate where further information is required. Application of the method is proposed as a decision support in the integrated development of products, informed purchasing and for regulatory purposes.     

Survey for the occurrence of antifouling paint booster biocides in the aquatic environment of Greece

Since the restriction imposed by European Union regulations on the use of TBT-based antifouling paints on boats below 25 m in length, new terms have been introduced in the 'small boat' market. Replacement products are generally based on copper metal oxides and organic biocides. Several studies have demonstrated the presence of these biocides in European ports and marinas of Spain, France, Germany and the United Kingdom. An extended survey of the antifouling biocides chlorothalonil, dichlofluanid, irgarol 1051 and sea-nine 211 was carried out in Greek ports and marinas of high boating activities from October 1999 to September 2000. The sampling sites were: Piraeus, Elefsina, Thessaloniki, Patras, Chalkida, Igoumenitsa, and Preveza (Aktio). The extraction of these compounds from the seawater samples was performed off-line with C18 solid phase extraction (SPE) disks while the determination was carried out with gas chromatography coupled to electron capture (ECD), thermionic (FTD) and mass spectroscopy (MS) detectors. The concentration levels of biocides were higher during the period from April to October. This seasonal impact depends on the application time of antifouling paints and mimic trends in the seasonal distribution of biocides in other European sites.