Biodegradation of third-generation organic antifouling biocides and their hydrolysis products in marine model systems.

The environmental fate for some selected antifouling biocides, dichlofluanid, tolylfluanid, tralopyril, and medetomidine, is relatively poorly understood with nearly all data derived from the assessment reports. Water/sediment systems and biofilms were used to determine biodegradation of the antifouling biocides. Dichlofluanid and tolylfluanid are known to hydrolyze to form DMSA (N,N-dimethyl-N'-phenylsulfamide) and DMST (N,N-Dimethyl-N'-(4-methylphenyl)sulfamide), respectively. DMSA did not show biodegradation, but it was shown to transform abiotically into N,N-dimethylsulfamide (N,N-DMS). In contrast, the structurally similar DMST did show biodegradation with a half-life of 5.78 days. The resulting transformation product of the biodegradation of DMST is also N,N-DMS. N,N-DMS accounted for the majority of the mass balance after 27 days in the water/sediment systems. Moreover, the biofilm systems also degraded both DMSA and DMST to N,N-DMS. The hydrolysis product of tralopyril, called BCCPCA (3-bromo-5-(4-chlorophenyl)-4-cyano-1 H-pyrrole-3-carboxylic acid), was not metabolized in the experiments and remained persistent. For this compound, a new log Kow of 2.47 was determined since the previously reported Kow value seemed to overestimate sediment partitioning. Medetomidine was removed from the water/sediment system, though, not significantly more than the control. However, a transformation product (medetomidine-acid) was detected in the incubation but not in the control, pointing to limited biodegradation. These results show that tolylfluanid can be rapidly removed by biodegradation in the marine environment, while dichlofluanid, tralopyril, and medetomidine remained in the system for a longer period of time. The prolonged stability of these biocides could mean that there is potential for accumulation in the environment. This potential is also there for the DMSA (dichlofluanid) and DMST (tolylfluanid) derived transformation product N,N-DMS, which was recalcitrant.

Abiotic fate of tolylfluanid and dichlofluanid in natural waters.

To prevent the growth of unwanted organisms on ship hulls, antifouling paints, containing biocides such as tolylfluanid (N-[dichlor(fluor)methyl]sulfanyl-N-(dimethylsulfamoyl)-4-methylaniline) and dichlofluanid (N-(dichlorfluormethylthio)-N',N'-dimethyl-N-phenylsulfamid), are applied. There are concerns over their occurrence and fate in the marine environment due to long-term immersion in water. In the present study, the hydrolysis and photolysis of these compounds were investigated. Results showed that tolylfluanid and dichlofluanid hydrolyzed completely to their respective hydrolysis products DMST (N,N-dimethyl-N'-p-tolylsulfamide) and DMSA (N,N-dimethyl-N'-phenylsulfamide) in coastal water within 24 h. Furthermore, the transformation of tolylfluanid and dichlofluanid under natural sunlight was determined in selected marine waters (coastal water and sea water) in comparison to deionized water. The experiments revealed that photodegradation rates of DMST and DMSA in coastal water were higher than in sea water or deionized water. The indirect phototransformation of the hydrolysis products with selected reactive species (triplet state organic matter, singlet oxygen, and hydroxyl radicals) showed that DMST and DMSA mainly display triplet reactivity. The measured half-lives of the hydrolysis products in natural waters were 2.7 and 23 days, with DMST being considerably faster transformed than DMSA. However, several direct and indirect photoproducts have been newly identified and measured. DMS (N,N-dimethylsulfamide), was identified as the major phototransformation product in natural waters. It is generated by indirect photodegradation processes and exhibits potential persistence in the environment.

The occurrence of modern organic antifouling biocides in Danish marinas.

Antifouling biocides are known to leach out of paints and into the aquatic environment. There is currently a data gap on the occurrence of the current antifouling biocides, as legislative changes caused a change in the antifouling market. Therefore, a comprehensive monitoring study was performed across 13 Danish marinas, both waters and sediments were analyzed, including a transect and a study with seasonal resolution. Three biocides, i.e., Medetomidine, Tralopyril, and DCOIT were not detected in any of the samples. More commonly found, in 11 of the 13 marinas, were the hydrolysis products of Dichlofluanid (DMSA) and Tolylfluanid (DMST). These biocides rapidly dropped in concentration and reached background levels around 200 m from the source. The antifouling biocide Irgarol 1051 was found in all sediment samples and half of all water samples. The concentrations of Irgarol were lower than previously monitored. The decrease can likely be attributed to legislative changes and its disapproval for use since 2016.