Antifouling paint booster biocides in the UK coastal environment and potential risks of biological effects

In the yachting sector of the UK antifouling market, organic biocides are commonly added to antifouling preparations to boost performance. Few data presently exist for concentrations of these compounds in UK waters. In this study the concentrations of tributyltin (TBT) and eight booster biocides were measured before and during the 1998 yachting season. The Crouch Estuary, Essex, Sutton Harbour, Plymouth and Southampton Water were chosen as representative study sites for comparison with previous surveys of TBT concentrations. Diuron and Irgarol 1051 were the only organic booster biocides found at concentrations above the limits of detection. Diuron was measured at the highest concentrations, whilst detectable concentrations of both Irgarol 1051 and diuron were determined in areas of high yachting activity (e.g. mooring areas and marinas). Maximum measured values were 1,421 and 6,740 ng/l, respectively. Lower concentrations of both compounds were found in open estuarine areas, although non-antifouling contributions of diuron may contribute to the overall inputs to estuarine systems. TBT was found to be below or near the environmental quality standard (EQS) of 2 ng/l for all samples collected from estuarine areas frequented by pleasure craft alone, but with much higher concentrations measured in some marinas, harbours and in areas frequented by large commercial vessels. Using the limited published environmental fate and toxicity data available for antifouling booster biocides, a comparative assessment to evaluate the risk posed by these compounds to the aquatic environment is described. TBT still exceeds risk quotients by the greatest margins, but widespread effects due to Irgarol 1051 and less so diuron cannot be ruled out (particularly if use patterns change) and more information is required to provide a robust risk assessment.     

Antifouling biocides in water and sediments from California marinas

Irgarol 1051 is a common antifouling biocide and is highly toxic to non-target plant species at low ng/L concentrations. We measured up to 254 ng/L Irgarol in water and up to 9 ng/g dry weight Irgarol in sediments from Southern California recreational marinas. Irgarol’s metabolite, M1, concentrations were up to 62 ng/L in water and 5 ng/g dry weight in sediments. Another antifouling biocide, diuron, reached up to 68 ng/L in water and 4 ng/g dry weight in sediments. The maximum Irgarol concentrations in water were greater than the Irgarol concentration recommended as the plant toxicity benchmark (136 ng/L), suggesting that Irgarol concentrations may be high enough to cause changes in phytoplankton communities in the sampled marinas. Irgarol concentrations measured in sediments were greater than calculated Environmental Risk Limits (ERLs) for Irgarol in sediments (1.4 ng/g). Antifouling pesticide accumulation in sediments may present a potential undetermined risk for benthic organisms.     

Probabilistic risk assessment of common booster biocides in surface waters of the harbours of Gran Canaria (Spain)

The presence of booster biocides in the aquatic environment has been associated with a risk to non-target species due to their proven toxicity. The aim of the present study was to determine the spatial and temporal distribution of common booster biocides in different harbours of the island of Gran Canaria (Spain) and evaluate, by means of a probabilistic risk assessment (PRA), the ecological risk posed by these compounds. With these objectives, a monitoring campaign was conducted between January 2008 and May 2009, collecting a total of 182 seawater samples. Four common booster biocides (TCMTB, diuron, Irgarol 1051 and dichlofluanid) were monitored. Diuron levels ranged between 2.3 and 203 ng/L and Irgarol 1051 between 2.4 and 146.5 ng/L. The ecological risk associated with these levels was always low, however, with probabilities of exceeding the 10th percentile of autotroph toxicity below 3.5%.     

Toxicities of antifouling biocide Irgarol 1051 and its major degraded product to marine primary producers

Irgarol 1051 (2-methythiol-4-tert-butylamino-6-cyclopropylamino-s-triazine) is an algaecide commonly used in antifouling paints. It undergoes photodegradation which yields M1 (2-methylthio-4-tert-butylamino-6-amino-s-triazine) as its major and most stable degradant. Elevated levels of both Irgarol and M1 have been detected in coastal waters worldwide; however, ecotoxicity effects of M1 to various marine autotrophs such as cyanobacteria are still largely unknown. This study firstly examined and compared the 96 h toxicities of Irgarol and M1 to the cyanobacterium Chroococcus minor and two marine diatom species, Skeletonema costatum and Thalassiosira pseudonana. Our results suggested that Irgarol was consistently more toxic to all of the three species than M1 (96 h EC50 values: C. minor, 7.71 μg L⁻¹ Irgarol vs. >200 μg L⁻¹ M1; S. costatum, 0.29 μg L⁻¹ Irgarol vs. 11.32 μg L⁻¹ M1; and T. pseudonana, 0.41 μg L⁻¹ Irgarol vs. 16.50 μg L⁻¹ M1). Secondly, we conducted a meta-analysis of currently available data on toxicities of Irgarol and M1 to both freshwater and marine primary producers based on species sensitivity distributions (SSDs). Interestingly, freshwater autotrophs are more sensitive to Irgarol than their marine counterparts. For marine autotrophs, microalgae are generally more sensitive to Irgarol than macroalgae and cyanobacteria. With very limited available data on M1 (i.e. five species), M1 might be less toxic than Irgarol; nonetheless this finding warrants further confirmation with additional data on other autotrophic species.     

A survey of antifoulants in sediments from Ports and Marinas along the French Mediterranean coast

Due to deleterious effects on non-target organisms, the use of organotin compounds on boat hulls of small vessels (<25 m) has been widely prohibited. The International Maritime Organisation (IMO) resolved that the complete prohibition on organotin compounds acting as biocides in antifouling systems should commence in 2008. As a result of restrictions on the use of organotin based paints, other antifouling formulations containing organic biocides have been utilised. This survey was conducted to assess the contamination of replacement biocides in the marine environment following the ban of TBT-based paints. Surface sediments samples were collected in the major ports and marinas along the France Mediterranean coastline (Cote d’Azur) and analysed for organotin compounds, Irgarol 1051, Sea-nine 211^TM, Chlorothalonil, Dichlofluanid and Folpet. Every port and marina exhibited high levels of organotin compounds, with concentrations in sediments ranging from 37 ng Sn g⁻¹dry wt in Menton Garavan to over 4000 ng Sn g⁻¹dry wt close to the ship chandler within the port of Villefranche-sur-Mer. TBT degradation indexes suggested that fresh inputs are still made. Among the other antifoulants monitored, only Irgarol 1051 exhibited measurable concentrations in almost every port, with concentrations ranging from 40 ng g⁻¹dry wt (Cannes) to almost 700 ng g⁻¹dry wt (Villefranche-sur-Mer, ship chandler).     

Assessment of tributyltin contamination in a shipyard area using a mussel transplantation approach

Mussels (Mytilus galloprovincialis) were transplanted to seven stations around a large shipyard for 126 days to evaluate tributyltin (TBT) contamination. Although the application of TBT-based paints to ships is totally banned in Korea, butyltin compounds were found to accumulate in mussels following transplantation. Concentrations of TBT and total butyltins in transplanted mussels near the shipyard were in the range of 40–350 ng Sn/g and 74–530 ng Sn/g on a dry weight basis, respectively. Obviously, low TBT concentrations (6.0–53 ng Sn/g dw) were determined in mussels at four stations outside the shipyard. A negative gradient of TBT concentrations and TBT portion to total butyltin concentrations were found in both the surface water and transplanted mussels according to distance from the shipyard. In addition, TBT concentrations in surface water and transplanted mussels showed significant correlation (r² = 0.71; p < 0.001). These results indicate that the shipyard still releases fresh TBT into surrounding waters even after TBT regulation in Korea, and mussel transplantation is useful in evaluating TBT contamination in shipyard area.     

The impact of legislation on the usage and environmental concentrations of Irgarol 1051 in UK coastal waters

In 2001, legislative measures were introduced in the UK to restrict usage of antifouling agents in small (<25 m) vessel paints to dichlofluanid, zinc pyrithione and zineb. This removed the previously popular booster biocides diuron and Irgarol 1051 from the market. To investigate the impact of this legislation, water samples were taken from locations where previous biocide levels were well documented. Results from analyses demonstrate a clear reduction in water concentrations of Irgarol 1051 (between 10% and 55% of that found during pre-restriction studies), indicating that legislation appears to have been effective. Although other booster biocides were screened for (chlorothalonil, dichlofluanid and Sea-Nine 211), they were below the limits of detection (<1 ng/l) in all samples. A survey of chandlers and discussions with legislative authorities supports these results and concurs the removal of Irgarol 1051 based paints from the market using simple regulations at a manufacturer level with little regulation at a retailer level.     

Contamination of the coastal waters of Bermuda by organotins and the triazine herbicide Irgarol 1051.

A study of the distribution of the 'booster' biocide 2-methylthio-4-tert-butylamino-6-cyclopropyl amino-s-triazine (Irgarol 1051) was carried out in the coastal waters of Bermuda. Irgarol 1051 concentrations (as determined by GC/MS) up to 590 ng l-1 have been measured within Hamilton Harbour. The data presented herein unequivocally demonstrate contamination of the coastal system of Bermuda by Irgarol 1051. Concurrently, TBT concentrations were measured and results indicate that levels are falling through legislated changes in antifouling treatments, from 220 ng l-1 in 1990 to < 20 ng l-1 (as Sn) by 1995, in the open water area of Hamilton Harbour. Concentrations of TBT immediately offshore from a boatyard were found to be > 600 ng l-1 (Sn), indicating continuing release due to painting operations and sediments in the area.     

Effects of new antifouling compounds on the development of sea urchin

Tributyltin oxide (TBTO) has been used worldwide in marine antifouling paints as a biocide for some time. However, it produced toxic effects, especially in marine water/sediment ecosystems. Consequently, its use in antifouling paints has been prohibited in many countries. In this study, the toxicity of alternative and/or new antifouling biocides compared with TBTO is assessed by a biological method. The effects of these chemicals on marine species have not been well studied. This paper assesses, comparatively, the effects of eight biocides on sea urchin eggs and embryos. The chemicals assessed were TBTO, Irgarol 1051, M1 (the persistent degradation product of Irgarol), Diuron, zinc pyrithione, 'KH101', 'Sea-Nine 211', and copper pyrithione. For these chemicals, toxicity appears to be in the order zinc pyrithione > Sea-Nine 211 > KH101 > copper pyrithione > TBTO > Diuron approximately = Irgarol 1051 > M1. Here, we show that zinc pyrithione, Sea-Nine 211, KH101, and copper pyrithione are much more toxic to sea urchins than TBTO or the other chemicals.     

Effects of tributyltin at concentrations below ambient levels in seawater on Caprella danilevskii (Crustacea: Amphipoda: Caprellidae)

Hatched juveniles of Caprella danilevskii (Crustacea: Amphipoda) were exposed to one of two concentrations of tributyltin (TBT) (1.1 and 10.7 ng TBT L⁻¹) for 49 d at 20 °C. These concentrations are near or below ambient levels in seawater. In both treatments and control, the survival rate was 100% at maturation, and >85% at the end of the experiments. Females reached maturation at 20 (median) to 21.5 d at instar VII, and repeated spawning 4–5 times during the experiment. The total number of juveniles per female decreased significantly from 39.5 in the control to 24.5 and 17.5 in 1.1 ng L⁻¹ and 10.7 ng L⁻¹ treatments, respectively. An earlier study reported that as the TBT concentration in seawater increased from a 0–10 ng L⁻¹ regime to a 10–20 ng L⁻¹ regime, the number of stations where Caprella spp. could be collected decreased along the coast of the Seto Inland Sea, of Japan. Thus, the present study indicates the possibility that the extremely low concentration of TBT measured in Japanese waters after 2000 lead to a reduction in reproductive success of Caprella spp.     

Spatial and temporal distribution of zooplankton related to the environmental conditions in the coral reef lagoon of New Caledonia,Southwest Pacific

The distribution of zooplanktonic prey of fish larvae was examined in three bays and two lagoonal stations in the Southwest lagoon of New Caledonia. Water column conditions were characterized by increasing chlorophyll a and particulate organic matter (POM) concentrations from the lagoon to the estuarine bay. The mean zooplankton settled volume and total density were significantly higher in the estuarine bay, reaching 35.1 mL m⁻³ and 3.5 × 10⁵ individuals m⁻³, respectively. The total zooplankton density also progressively increased along the sampling period. The composition of assemblages differed between the lagoon and the bays, and was similar in the three bays. Wind speed, surface temperature, chlorophyll a and POM explained these variations, as revealed by a co-inertia analysis (COIA). The prey preferred by fish larvae, i.e. small crustaceans and small copepods, were more abundant in bays. Sheltered bays, most influenced by terrigenous inputs, are likely to provide the best feeding conditions.     

Quantities,composition, and sources of beach debris in Korea from the results of nationwide monitoring

This study assessed the levels of marine debris pollution and identified its main sources in Korea. The surveys were bimonthly conducted by NGO leaders and volunteers on 20 beaches from March 2008 to November 2009. The quantities of marine debris were estimated at 480.9 (±267.7) count ⋅ 100 m⁻¹ for number, 86.5 (±78.6) kg ⋅ 100 m⁻¹ for weight, and 0.48 (±0.38) m³ ⋅ 100 m⁻¹ for volume. The level of marine debris pollution on the Korean beaches was comparable to that in the coastal areas of the North Atlantic ocean and South Africa. Plastics and styrofoam occupied the majority of debris composition in terms of number (66.7%) and volume (62.3%). The main sources of debris were fishing activities including commercial fisheries and marine aquaculture (51.3%). Especially styrofoam buoy from aquaculture was the biggest contributor to marine debris pollution on these beaches.     

Extreme irgarol tolerance in an Ulva lactuca L. population on the Swedish west coast

The herbicide irgarol 1051 is commonly used on ship hulls to prevent growth of algae, but as a component of self-eroding paints it can also spread in the surrounding waters and affect non-target organisms. The effect of irgarol on settlement and growth of zoospores from the marine macro algae Ulva lactuca from the Gullmar fjord on the Swedish west coast was investigated in the present study. The zoospores were allowed to settle and grow in the presence of irgarol, but neither settlement – nor growth inhibition was observed at concentrations of up to 2000 nmol l⁻¹. This is between 10 and 100 times higher than effect concentrations reported earlier for algae. Irgarol also induced the greening effect (4-fold increase in chlorophyll a content) in the settled zoospore/germling population, typical for photosystem II inhibitors like irgarol. This study support previous findings that irgarol constitutes a selection pressure in the marine environment.     

Imposex levels and concentrations of organotin compounds (TBT and its metabolites) in Nassarius nitidus from the Lagoon of Venice

Specimens of Nassarius nitidus were collected in seven stations of the Venice Lagoon to assess the levels of tributyltin (TBT) and its metabolites monobutyltin and dibutyltin in the tissues and monitor their effect on organisms, in particular the phenomenon of imposex (superimposition of male sexual characteristics on females). The following values of population indices were found: vas deferens sequence: 1.2 ± 0.7–4.0 ± 0.5; relative penis length: 6–47%. The least impacted station was situated in the northern part of the Lagoon, where females without imposex were found and Butyltin (BuTs) concentrations in the organisms (average sum of BuTs = 43 ± 14 ng Sn g⁻¹ w.) were significantly lower than in the other stations (range of average sum of BuTs: 101 ± 22–217 ± 27 ng Sn g⁻¹ d.w.). Population indices were found to be related to the TBT content in the tissues. In particular VDSI had a significant logarithmic correlation: r = 0.95, n = 8, p < 0.05.     

Polycyclic aromatic hydrocarbons in the coastal water,surface sediment and mullet Liza klunzingeri from northern part of Hormuz strait (Persian Gulf)

The concentrations of 16 polycyclic aromatic hydrocarbons (PAHs) were determined in mullet (Liza klunzingeri), water and sediment from northern part of Hormuz strait (Persian Gulf). The concentration levels of total PAHs in L. klunzingeri, water and sediment were 133.99–268.57 ng g⁻¹ dry weight, 3.12–5.88 ng l⁻¹ and 42.29–228.9 ng g⁻¹ dry weight, respectively. Based on isomer ratios, analysis of the PAHs source in the sediment demonstrated that the PAHs come from pyrogenic and petrogenic origin. Risk assessment showed PAHs threshold concentrations to occasionally be exceeded in the study area.     

Atmospheric polychlorinated biphenyl (pcb) inputs to a coastal city near the marmara sea

Recent studies have shown that polychlorinated biphenyl (PCB) levels are high in coastal sites. Various types of deposition events, including dry deposition, air–water exchange and wet deposition, were analyzed as part of the study to illustrate the pollution level. The atmospheric levels and deposition mechanisms of 82 PCBs were investigated in Mudanya, a coastal city in Turkey. A total of 175 samples and 112 blanks were collected. Air–water exchange and particle phase dry deposition fluxes were 120 ± 90 ng/m²-d and 125 ± 160 ng/m²-d, respectively. The wet-dry deposition sampler (WDDS) consisted of two reservoirs, wet and dry. Collected with the WDDS, the dry deposition flux was 21 ± 20 ng/m²-d, and the wet deposition fluxes (during the rainy period) were 145 ± 130 ng/m²-d and 195 ± 270 ng/m²-d for the dissolved and particulate phases, respectively. Mass transfer coefficients (MTCs), dry deposition velocities and washout ratios were calculated and compared with the literature values.     

Regional distribution of halogenated organophosphate flame retardants in seawater samples from three coastal cities in China

Thirteen samples of seawater were collected from Yellow Sea and East China Sea near Qingdao, Lianyungang, and Xiamen, China. They were analyzed for halogenated organophosphorus flame retardants (OPFRs). The compounds selected for detection were Tris(2-chloroethyl) phosphate (TCEP), Tris(2-chloroisopropyl) phosphate (TCPP), Tris (1,3-dichloro-2-propyl) phosphate (TDCPP), and Tris(2,3-dibromopropyl) phosphate (TDBPP). The total concentrations ranged from 91.87 to 1392 ng/L and the mean concentrations of these four chemicals were 134.44, 84.12, 109.28, and 96.70 ng/L, respectively. TCEP exhibited the highest concentrations, although concentrations of TCPP and TDCPP were also fairly high in Lianyungang and Xiamen. Generally, Lianyungang was the most heavily polluted district, with very high concentrations of TCEP at LYG-2 (550.54 ng/L) and LYG-4 (617.92 ng/L). The main sources of halogenated OPFRs were municipal and industrial effluents of wastewater treatment plants in the nearby economic and industrial zones.     

Butyltin compounds,sterility and imposex assessment in Nassarius reticulatus (Linnaeus, 1758), prior to the 2008 European ban on TBT antifouling paints,within Basque ports and along coastal areas

Levels of imposex (superimposition of male characters, upon females) and the presence of sterile females are assessed in the gastropod Nassarius reticulatus (L.), at 35 locations in the Basque Country. At 18 of these localities, organotin bioaccumulation (tributyltin (TBT); dibutyltin; monobutyltin) was evaluated, using isotope dilution GC–ICP–MS. Higher imposex levels and TBT body burden were found in confined harbours, with large vessel traffic or the presence of an offshore fleet. The highest values were found for the port of Pasaia, near to a shipyard (a relative penis size index of up to 92%, and TBT body burden up to 405 ng g^?1 – given on a dry weight basis as Sn). Imposex effects were evaluated also in parasitized females, at some of the sampling sites. The percentage of presence of c-type Vas Deferens sequence stages (i.e., with vas deferens beginning at the oviduct opening) was higher in parasitized females. In turn, there was an absence of highly convoluted oviduct in parasitized females.     

Geochemical modelling and speciation studies of metal pollutants present in selected water systems in South Africa

Metal pollutants in water poses great threats to living beings and hence requires to be monitored regularly to avoid loss of lives. Various analytical methods are available to monitor these pollutants in water and can be improved with time. Modelling of metal pollutants in any water system helps chemists, engineers and environmentalists to greatly understand the various chemical processes in such systems. Water samples were collected from waste water treatment plant and river from highlands close to its source all the way to the ocean as it passing through areas with high anthropogenic activities. Pre-concentration of pollutants in the samples was done through acid digestion and metal pollutants were analysed using inductively coupled plasma-optical emission spectra (ICP-OES) to determine the concentration levels. Metal concentrations ranged between 0.1356–0.4658 mg/L for Al; 0.0031–0.0050 mg/L for Co, 0.0019–0.0956 mg/L for Cr; 0.0028–0.3484 mg/L for Cu; 0.0489–0.3474 mg/L for Fe; 0.0033–0.0285 mg/L for Mn; 0.0056–0.0222 mg/L for Ni; 0.0265–0.4753 mg/L for Pb and 0.0052–0.5594 mg/L for Zn. Modelling work was performed using PHREEQC couple with Geochemist’s workbench (GWB) to determine speciation dynamics and bioavailability of these pollutants. Modelling thus adds value to analytical methods and hence a better complementary tool to laboratory-based experimental studies.     

Distribution,origin, and potential toxicological significance of polycyclic aromatic hydrocarbons (PAHs) in sediments of Kaohsiung Harbor,Taiwan

Sediment samples were collected from 12 locations of Kaohsiung Harbor, Taiwan and analyzed for polycyclic aromatic hydrocarbons (PAHs). Total PAH concentrations varied from 472 to 16,201 ng g⁻¹ dry weight. The highest PAH concentrations were from the industrial zone docks situated in south Kaohsiung Harbor. Diagnostic ratios showed that the possible source of PAHs in the industrial zone dock could be coal combustion while in the other zones it could be petroleum combustion. The toxic equivalent concentrations (TEQ^carc) of PAHs varied from 55 to 1964 ng TEQ g⁻¹ dry weight. Higher total TEQ^carc values were found at industrial zone docks (from 1404 to 1964 ng TEQ g⁻¹ dry weight). As compared with the US Sediment Quality Guidelines (SQGs), the observed levels of PAHs at industrial zone docks exceeded the effects range low (ERL), and could thus cause acute biological damage. However, the lower levels of PAHs at the other zones would probably not exert adverse biological effects.