Cationic surfactants have a strong affinity to sorb to phospholipid membranes and thus possess an inherent potential to bioaccumulate, but there are few measurements of bioconcentration in fish. We measured the bioconcentration of 10 alkylamines plus two quaternary ammonium compounds in juvenile rainbow trout at pH 7.6, and repeated the measurements at pH 6.2 for 6 of these surfactants. The BCF of the amines with chain lengths <= C-14 was positively correlated with chain length, increasing similar to 0.5 log units per carbon. Their BCF was also pH dependent and approximately proportional to the neutral fraction of the amine in the water. The BCFs of the quaternary ammonium compounds showed no pH dependence and were >2 orders of magnitude less than for amines of the same chain length at pH 7.6. This indicates that systemic uptake of permanently charged cationic surfactants is limited. The behavior of the quaternary ammonium compounds and the two C-16 amines studied was consistent with previous observations that these surfactants accumulate primarily to the gills and external surfaces of the fish. At pH 7.6 the BCF exceeded 2000 L kg(-1) for 4 amines with chains >= C-13, showing that bioconcentration can be considerable for some longer chained cationic surfactants.

Fish bioconcentration factors (BCFs) are commonly used in chemical hazard and risk assessment. For neutral organic chemicals BCFs are positively correlated with the octanol-water partition ratio (K-OW), but K-OW is not a reliable parameter for surfactants. Membrane lipid-water distribution ratios (D-MLW) can be accurately measured for all kinds of surfactants, using phospholipid-based sorbents. This study first demonstrates that D-MLW values for ionic surfactants are more than 100 000 times higher than the partition ratio to fish-oil, representing neutral storage lipid. A non-ionic alcohol ethoxylate surfactant showed almost equal affinity for both lipid types. Accordingly, a baseline screening BCF value for surfactants (BCFbaseline) can be approximated for ionic surfactants by multiplying D-MLW by the phospholipid fraction in tissue, and for non-ionic surfactants by multiplying D-MLW by the total lipid fraction. We measured D-MLW values for surfactant structures, including linear and branched alkylbenzenesulfonates, an alkylsulfoacetate and an alkylethersulfate, bis(2-ethylhexyl)-surfactants (e.g., docusate), zwitterionic alkylbetaines and alkylamine-oxides, and a polyprotic diamine. Together with sixty previously published D-MLW values for surfactants, structure-activity relationships were derived to elucidate the influence of surfactant specific molecular features on D-MLW. For 23 surfactant types, we established the alkyl chain length at which BCFbaseline would exceed the EU REACH bioaccumulation (B) threshold of 2000 L kg(-1), and would therefore require higher tier assessments to further refine the BCF estimate. Finally, the derived BCFbaseline are compared with measured literature in vivo BCF data where available, suggesting that refinements, most notably reliable estimates of biotransformation rates, are needed for most surfactant types.

Bioaccumulation assessment is important for cationic surfactants in light of their use in a wide variety of consumer products and industrial processes. Because they sorb strongly to natural surfaces and to cell membranes, their bioaccumulation behavior is expected to differ from other classes of chemicals. Divided over two mixtures, we exposed rainbow trout to water containing 10 alkyl amines and 2 quaternary alkylammonium surfactants for 7 days, analyzed different fish tissues for surfactant residues, and calculated the tissues' contribution to fish body burden. Mucus, skin, gills, liver, and muscle each contributed at least 10% of body burden for the majority of the test chemicals. This indicates that both sorption to external surfaces and systemic uptake contribute to bioaccumulation. In contrast to the analogue alkylamine bases, the permanently charged quaternary ammonium compounds accumulated mostly in the gills and were nearly absent in internal tissues, indicating that systemic uptake of the charged form of cationic surfactants is very slow. Muscle-blood distribution coefficients were close to 1 for all alkyl amines, whereas liver-blood distribution coefficients ranged from 13 to 90, suggesting that the dominant considerations for sorption in liver are different from those in blood and muscle. The significant fraction of body burden on external surfaces can have consequences for bioaccumulation assessment.