ABSTRACT The echluroid worm Urechis caupo is one of the many marine invertebrates that is able to live and reproduce in a polluted environment. One proposed explanation for this worm's resistance to pollutants is the multixenobiotic resistance (MXR) mechanism, whereby a protein in the cell membrane pumps a wide variety of moderately hydrophobic compounds out of the cells. This protein is analogous to multidrug resistance (MDR) in mammalian cells which provides mammalian cells with multidrug resistance to chemotherapeutic agents. These data support the role of MXR as a protective mechanism for marine invertebrates, suggest bioassays for pollutants, and propose that the phenomenons of hormesis and multixenobiotic resistance are related. INTRODUCTION Multidrug resistance, or multixenobiotic resistance, is one phenomenon that is responsible for both the resistance of tumor cells to chemotherapy drugs, and the ability of marine organisms to survive in highly polluted habitats. This resistance is believed to be directly related to levels of expression of the MDR protein in mammals, and to an immunologically related protein of 140-145 KD in marine invertebrates (1). For a protein with such diverse effects as are created by MDR, one can easily imagine the importance of scientific research of MXR to the fields of medicine, toxicology, and marine biology. The MDR protein is a transmembrane protein of 1280 amino acids with two equivalent ATP binding sites, only one of which must be occupied for transport (2). A protein immunologically related to the MDR protein in mammals has been shown to exist in the echiuroid worm Urechis caupo (3) which lives and reproduces in U¬ shaped burrows in the mud flats at Moss Landing. Urechis uses peristaltic contractions of its muscular body to move water through the burrows, thereby replenishing food and oxygen, and removing wastes that have seeped in from the surrounding sediment. Previous studies have shown that hydrogen sulfide, a highly toxic compound, can also accumulate in sediments of shallow marine bays such as the Elkhorn Slough at Moss Landing (4). In this study I assessed MR activity using rhodamine fluorescence assays which measure the accumulation of rhodamine dye, a substrate of the mammalian multidrug transporter (5). Urechis embryos incubated with rhodamine and a competitive inhibitor of the MXR protein fluoresce more brightly than embryos in the dye alone. Verapamil is a potent inhibitor of the MDR protein (6,7) and it was used as a known inhibitor in the rhodamine assays. The second part of this study asked whether MDR activity can protect embryos that develop in supposedly polluted sediment water or in the presence of known cytotoxic compounds. For this study I devised an assay in which Urechis caupo embryos or Strongylocentrotus purpuratus embryos are allowed to develop in sediment pore water in the presence, or absence of an MXR inhibitor. If compounds that are substrates for the MXR protein are present in the pore water, competition between those substrates and the NXR inhibitor would result in higher levels of substrates inside the cells and, possibly, abnormal development. Through the use of these two methods, I investigated the presence of substrates for the MXR protein in sediment from Moss Landing. In addition the effectiveness of various chemicals as competitive inhibitors of MXR in the developmental assay, and the effects of sediment on the development of Urechis caupo and Strongylocentrotus purpuratus embryos were determined. The results of this work revealed the phenomenon of hormesis, in which a stress response is stimulated in an organism that is exposed to non-toxic levels of a toxin (8). I also found evidence which suggests that verapamil is toxic at very low levels (.022 uM), and that this compound would give misleading results when used as a competitive substrate in developmental assays. On the other hand, my work suggests that rhodamine B might be a useful competitive substrate in developmental assays, because it is a known substrate of the MXR protein and it is less toxic than verapamil. MATERIALS AND METHODS Adult Urechis caupo were collected at the mud flats in Moss Landing, CA on two different dates, April 9, 1993 or May 28, 1993. The worms were maintained in tanks with a constant source of fresh sea water. Urechis were spawned, and the eggs were fertilized according to Gould (9). Strongylocentrotus purpuratus were collected at Point Arena, CA, and they were maintained with a constant flow of fresh sea water according to Czihak and Peter (10). For the rhodamine fluorescence assays 10 ul of 1mM rhodamine B was added to 10 ml of eggs, which made a final concentration of luM. The eggs were divided into 2 test tubes of 5 ml each, and either 22pM of verapamil or 25 ul of sediment extract was added to one of the test tubes. The embryos were incubated for one hour at 16’C. The eggs were then washed into filtered sea water and the fluorescence was measured using a Zeiss epifluorescence microscope fitted with a photosensor. The light emitted by the embryos was expressed by a voltmeter as relative fluorescence units. For the developmental assays the eggs were fertilized in type GS.22um millipore filtered sea water (MFSW) and incubated in their respective solutions at 16’C. These solutions were combinations of the following: MFSW, pore water, verapamil (.022 uM or .044 uM), rhodamine B (1.25 uM), and emetine (.0025 uM or .005 uM). In cases where pore water was used, it was used in equal amounts with the MFSW. Pore water was removed from the sediment by vigorously shaking it for two minutes, and centrifuging it at high speed for one minute. To reduce water loss by evaporation, the beakers containing the Urechis embryos were partially covered with Parafilm, whereas the S. purpuratus embryos were constantly stirred to prevent crowding and anoxia. At the designated times an aliquot of embryos was removed, inspected for abnormalities under the microscope, counted and discarded. If the embryos had hatched they were fixed with one drop of 37% formaldehyde before counting and inspection. Abnormal development for sea urchin embryos included delayed cleavage, lysed cells, disorganized cells, exogastrulation, and little or no movement compared to controls. In the developmental assay for Urechis, abnormal development was based on the same critéria, except that once the embryos were swimming, continuous spinning to only one side was considered abnormal, in addition to little movement compared to controls. Sediment samples were collected at Moss Landing, at the site of adult worm collection. They were frozen at -80 C within one hour of collection, and thawed prior to use. For some experiments extractions from the pore water, or directly from the sediment were done by mixing with chloroform:methanol (2:1). The solvent phase was removed to a clean tube and evaporated. The remaining residue was dissolved into 200 ul of 95% ethanol and used in the rhodamine or development assays. RESULTS Rhodamine Assays: The embryos incubated with 1 uM rhodamine plus 22uM verapamil have average fluorescence levels that are 15.6% higher than those embryos incubated in only MFSW and rhodamine. This percentage is a measure of the effect of verapamil on MXR activity. The embryos incubated in luM rhodamine plus 25 ul of sediment extract fluoresced an average of 11.65% more than the embryos that were incubated in only MFSW plus rhodamine. This indicates that there are substrates for MDR in the sediment, but that they are not in as high a concentration as the 22uM verapamil substrate. One should also note that the intensity of fluorescence for the sediment extract varied from 5.5% to 17.8%, indicating that the levels of substrates in the sediment are not constant. S. purpuratus Developmental Assays: The embryos incubated in pore water, or water taken from the sediment after centrifugation, averaged 51.8% more abnormalities than the embryos that developed in MFSW. It is believed that this high level of abnormalities in the pore water can be attributed to the combinatory effect of toxins in the pore water, and the lack of an MXR protein to protect the sea urchin embryos. Less clear results were found in the developmental assay done with a sediment extract. The sediment extract was made by evaporating with chloroform: methanol (2:1), and then dissolving the residue in ethanol. Although the embryos that were incubated in sediment extract averaged 59.7% higher abnormalities than those that developed in only MFSW, the control embryos that were incubated in an equal amount of ethanol also had very high abnormality, which indicates that the ethanol was affecting development. The numbers for S. purpuratus and Urechis developmental assays were calculated by taking the average number of abnormalities in each group, subtracting the difference between the two groups being compared, and multiplying that number by 100 to get the % abnormality. U. caupo Developmental Assays with Verapamil 022 UM Or.044 UM): The first assay done with .022 uM of verapamil showed a difference of only .66% between the average abnormality level of the embryos developing in pore water plus verapamil and those embryos developing in MFSW plus verapamil. However, when the concentration of verapamil was doubled to .044 uM the difference in abnormality levels increased to 18%. It is important to note that after the sixth cleavage the controls of only verapamil increase in abnormalities until they have a higher % abnormal than the experimentals. One should also note that the % abnormal for the embryos in the MFSW is higher than it is for the embryos developing in only pore water. This result led to the idea that the phenomenon of hormesis is related to the activity of MXR. U. caupo Developmental Assays with Emetine (0025 uM or 005 UM): The embryos that developed in pore water plus .0025 uM of emetine averaged only 3.6% more abnormalities than did the embryos that developed in MFSW plus an equal concentration of emetine. However, when the concentration of emetine was doubled, those embryos that were incubated in pore water plus emetine averaged 19% more abnormalities than did those embryos that were incubated in only MFSW plus emetine. As in the developmental assay with verapamil, the levels of abnormalities for all the embryos increased after the sixth cleavage. More importantly, by the sixth cleavage the % abnormal for the embryos in the MFSW was higher than it was for those developing in only pore water, which provides further evidence for hormesis. U. caupo Developmental Assay with Rhodamine B (1.25 UM: The embryos that developed in pore water plus 1.25 uM of rhodamine averaged 8.8% more abnormalities than those embryos that developed in MFSW plus the same concentration of rhodamine. As in the previous assays with Urechis, those embryos that developed in only MFSW eventually averaged a higher % abnormality 10 than did those embryos that developed in only pore water. Although the abnormalities of the control group increased after the sixth cleavage, rhodamine proved overall to be much less toxic than either verapamil or emetine. 11 DISCUSSION In this study and previous studies (3), it has been shown that the efflux of rhodamine B dye is decreased in the presence of pore water or extractions of sediment collected from the mud flats at Moss Landing. Based on rhodamine fluorescence assays that I have done, which reveal varying degrees of rhodamine efflux inhibition, it is possible to conclude that although there is indirect evidence of MXR substrates in the sediment, the levels of these substrates vary. These different levels may be depend on the time of day or of year that the sediment is collected, the location of the sediment, the biological make-up of the sediment and/or the size of the sediment grains. The developmental assays done with Strongylocentrotus purpuratus provide evidence that toxic substrates for the MXR protein exist in the sediment collected from Moss Landing. S. purpuratus has been shown to lack the MXR protein (3), and this species of sea urchin develops abnormally in the sediment which Urechis caupo inhabits. Therefore, it is reasonable to propose that the abnormal development in S. purpuratus is due to the absence of MXR in this species of sea urchin, and that MXR is a protective mechanism for inhabitants of the Moss Landing mud flats. The developmental assays done with Urechis demonstrate that the use of verapamil as a competitive substrate should be avoided due to its toxic effects at concentrations as low as .022 uM. Furthermore, it seems that rhodamine B may be used instead of verapamil as a competitive inhibitor of MXR, because it is less toxic and it is a known substrate of the MXR protein. These assays could potentially become important methods of environmental xenobiotic¬ risk assessment and toxicology; especially in the case where the effect of a specific toxin on development is known and can be detected in embryos developing under the influence of a known competitive inhibitor of the MXR protein. Perhaps the most interesting and novel results in this project are those that provide evidence for the phenomenon of hormesis occurring in developing Urechis embryos. Hormesis is the condition where low levels of a toxin stimulate a stress response in an organism which instills, in that organism, some form of beneficial effect(8). The lower numbers of abnormal embryos developing in pore water than those developing in MFSW are evidence of hormesis. However, further study is necessary to determine if the form of hormesis that is occurring involves induction or activation of higher levels of the MXR protein. If the levels of toxins in the environment of Urechis caupo are affecting the expression or activation of the MXR protein, then measurements of this protein may one day be used as biomarkers of water pollution. 13 ACKNOWLEDGEMENTS I would like to thank my advisor Dr. David Epel for sharing his wonderful enthusiasm for development, and his valuable insights into my project. Sincere thanks also go to Barbara Holland Toomey, for taking the time and patience to share her knowledge of multixenobiotic resistance in Urechis caupo, and the methods for studying this phenomenon. Thanks to Chris Patton for his technical assistance, as well as his "pre-med munchkin" jokes. Finally, I would like to thank my colleague Joyce Chen, whose wit and encouragement made an adventure out of the long days in lab. LITERATURE CITED 1. Kurelec, B., Critical Reviews in Toxicology 22(1), 23-43 (1992). 2. Gottesman M. M., and Pastan, I., J. Biol. Chem. 263, 12163- 12166 (1988). 3. Toomey, B. H., and Epel, D., (submitted). Multixenobiotic transport in Urechis embryos: protection from environmental toxins. 4. Julian, D. and Arp, A. J., J. Comp. Physiol. B. 162, 59-67 (1992). 5. Mierendorf, R. C., C. Percy, and R. A. Young, in Methods in Enzymology, S. L. Berger and A. R. Kimmel, Eds. (Academic Press, Inc., Orlando, 1987) pp. 458-469. 6. Cornwell, M. M., Pastan, I. and Gottesman, M. M., J. Biol. Chem. 262, 2166, (1987). 7. Hollt, V., Kouba, M., Dietel, M. and Vogt, G., Biochem. Pharmacol. 43, 2601, (1992). 8. Dictionary of Scientific and Technical Terms, (McGraw-Hill Book Company, New York, 1978), p. 764. 9. Gould, M., Methods in Developmental Biology, Wilt, F. H. and Wessells, N. K., Eds. (Thomas Y. Crowell Co. New York, 1967) pp. 163-171. 10. Czihak, G. and Peter, R., Eds. The Sea Urchin Embryo, (Springer¬ Verlag, New York, 1975) pp. 11-23. 11. Newby, W., Memoirs of the American Philosophical Society, vol. 16. Independence Square, Philadelphia, Pa., (1940). 15 FIGURE LEGENDS Figure 1. Rhodamine fluorescence vs. incubation solution. The first column represents eggs that were incubated in only rhodamine dye, and the second column represents eggs that were incubated with rhodamine dye plus verapamil for the same amount of time. The third column is the same as the first, just rhodamine dye incubation, and the last one represents an incubation of rhodamine dye and sediment extract. Figure 2. Rhodamine fluorescence vs. incubation solution. The first column represents eggs that were incubated in only rhodamine dye, and the second column represents eggs that were incubated with rhodamine dye plus verapamil for the same amount of time. The third column is the same as the first, just rhodamine dye incubation, and the last one represents an incubation of rhodamine dye plus sediment extract. Figure 3. Examples of normal and abnormal development in S. purpuratus. The photographs were taken at the 16 cell stage of embryos from the same batch of eggs. The normal embryo was developing in MFSW, and the abnormal embryo, which exhibits delayed cell cleavage, was developing in pore water. Figure 4. Developmental assay with % abnormal plotted against time in hours after fertilization. There is little difference between the lines for the sediment extract and the ethanol, indicating that the ethanol was affecting development. Figure 5. Examples of normal and abnormal development in Urechis caupo embryos. The photographs were taken at the swimming trocophore stage of embryos from the same batch of eggs. The 16 normal embryo was developing in MFSW, and the abnormal embryo was developing in pore water plus .044 uM verapamil. Figure 6. Developmental assay with % abnormal plotted against the cleavage stage for normally developing embryos as determined by Newby (11). Figure 7. Experiment was done and graphed in the same way as the experiment in figure 3, except that the concentration of verapamil was doubled. Figure 8. Developmental assay with % abnormal plotted against the cleavage stage for embryos with normal development. Figure 9. Experiment was done and graphed in the same way as the experiment in figure 5, except that the concentration of emetine was doubled. Figure 10. Developmental assay with % abnormal plotted against the cleavage stage for embryös with normal development. 17 Figure 1. 0.14 0.02 0.00 Rhodamine Assay with Sediment Extract Ver + Ver - SD extr + SD extr Figure 2. 4/22 Rhodamine Fluorescence Assay with Sediment Extract 0.10 0.08 0.06 004 0.02 0.00 Figure 3. Examples of Normal and Abnormal Development in S. purpuratus A normal embryo at the 16 cell stage. An abnormal embryo photographed at the same time. Figure 4. 5/11 puratus Assay with Sediment 100 90- L 80 A 70- 50 40 30- 20 101 o k k- 5 10 15 20 25 30 35 40 45 50 time (hours after fertilization) —2— mfsw — w —0— sd. extract 5Oul ——— EtOH (99%) 50 E Figure 5. Examples of Normal and Abnormal Development in Urechis aupo A normal embryo at the swimming trocophore stage An abnormal embryo photographed at the same time Figure 6. 5/19 Urechis Assay with Verapamil (.022 uM) 100 90 - 60 50 0 30 20 107 o S 6 10 8 cleavage —— mfsw —— DW —0— pw + Ver er Figure 7. 5/19 Urechis Assay with Verapamil (.044 uM) 100 90 80- 70- 60 —2— mfsw —— pw 50 —0— pw + Ver 40 —— + Ver 30- 20 10 S o 8 cleavage Figure 8. 5/26 Urechis Assay with Emetine (.0025 uM) 100 90- 80 70 60 50 40 30 20 10 f — O + cleavage —2— mfsw Pw —— pw + Em — + Em 10 Figure 9. 5/26 Urechis Assay with Emetine (.005 yM) 100 80 70 60 50 10 30 20 10 — 0+ 6 8 10 4 cleavage —— mfsw — w — pw +Em — +Em Figure 10. 5/26 Urechis Assay with Rhodamine (1.25 uM) 100- 90 80: 70- 50 40 30 20 10 o 6 8 10 cleavage —— mfsw PW — W + R —— +R