Reminiscence of Forty Years of Environmental Chemistry

Bulletin of Environmental Contamination and Toxicology, Nov 2016

Vladimir Zitko

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Reminiscence of Forty Years of Environmental Chemistry

Reminiscence of Forty Years of Environmental Chemistry 0 St. Andrews , NB , Canada Editor-in-Chief Comment Please take the time to read this interesting retrospective that highlights Dr. Vladimir Zitko's extensive career in the ield of environmental chem - istry. Note that nine of his papers referenced in this retrospective were published in BECT during the 1970s. After working on blood anti-clotting substances from phospholipids in the R&D laboratories of Canada Packers Limited in Toronto in 1968, I accepted the position of a chemist at the Fisheries Research Board of Canada Biological Station in St. Andrews, New Brunswick. In water pollution research, the Station staf monitored copper and zinc concentrations in the Northwest Miramichi River and their efect on the movement of Atlantic salmon. I joined a team studying the movement of salmon through the estuary, started looking at dissolved organics and found pentachlorophenol in the eluent of a wood preserving plant (Zitko and Carson 1969a). In minor projects, the decomposition of thiosulfate was identiied as the cause of a puzzling acidii - cation of a New Brunswick river (Zitko and Carson 1969b), and lignosulfonates were found in the Mactaquac impoundment on the Saint John River (Zitko 1970a, b, c). Then came four nondiscretionary projects. The 'red herring' episode in Placentia Bay, Newfoundland resulted in a study of the toxicity of yellow phosphorus to Atlantic herring (Zitko et al. 1970a, b). Yellow phosphorus is extremely lethal and causes subcutaneous bleeding, turning the herring red. A major residual oil spill in Chedabucto Bay prompted the development of a method to measure it in aquatic fauna (Zitko 1970a, b, c). The concentrations of the oil were around 100 μg/g. A concern about mercury in the - environment led to a survey of methyl mercury in aquatic fauna (Zitko et al. 1971). A widespread contamination was found. A method was devised for removal of methyl mercury from ish meal (Zitko 1971a, b). Forest spraying by fenitrothion provided an opportunity to test its efect on ish brain acetylcholine esterase (Zitko et al. 1970a, b). No signiicant efects were found. Finally, I could start work of my own choice. Homogeneous solutions of PCBs were prepared by nonionic surfactants to determine the PCBs toxicity to juvenile salmon (Zitko 1970a, b, c). PCBs were not very acutely toxic and the surfactants did not prevent their accumulation in ish. The presence of PCBs was wide-spread in freshwater and marine ishes (Zitko 1971a, b). Unusually high concentrations of PCBs in hatchery-reared Atlantic salmon led to the discovery of 6.5% of the PCB preparation ‘Aroclor 1254’ in the antifouling paint of hatchery tanks (Zitko and Hutzinger 1972). Long-chain chlorinated parains (Zitko 1980a, b, c) replaced Aroclor 1254 in the paint. Their presence in reformulated paint was conirmed by dechlorination (Zitko 1974). They were less accumulated by ish, but further work had to wait for better instrumentation. In the meantime, all PCB congeners became available and a reference to individual congeners required consultation of long tables. A shorthand description was suggested (Zitko 1983), but iswas not popular. Polychlorinated terphenyls (Zitko et  al. 1972) were detected in herring gulls, but not in cormorants. Accordingly, it appeared that they may not be as widely spread in the environment as PCBs. Further work had to wait for better methods. Chloroalkylene 12, which, in addition to chlorine also contains isopropyl groups, was developed by the industry to soften the environmental efects of PCBs. It did (Zitko and Carson 1977), but has not become widely used. Further studies of organohalogen compounds of potential concern to isheries included hexahlorobenzene and hexabromoben zene. The former was, but the latter was not accumulated by juvenile salmon (Zitko and Hutzinger 1976). Chlorinated diphenyl ethers (PDEs) behaviour was very similar to that of PCBs. The BDE conmgener proile in Atlantic herring was diferent from that in Baltic herring (Roots et al. 2009). Brominated toluenes were more persistent in ish than PDEs (Zitko and Carson 1977). Polybrominated biphenyls (PBBs) with six or fewer bromine atoms were taken up from water by the ish. All PBBs were taken up from food and some new less brominated congeners were found in the ish as well. (Zitko 1977). Mirex and Dechlorane 602 were taken up by salmon both from water and from food, while Dechloranes 603, 604 and Plus 25 only from food (Zitko 1980a, b, c). With the advent of the mass spectrometer, nonachlor and chlordane were found in aquatic fauna (Zitko 1978). Interestingly, these were the only pesticides present at much higher concentrations in a ‘sick’ bluein tuna. How ever, the tuna also contained components of toxaphene, not quantitated because of absence of standards (Zitko 1980a, b, c). Additional work included a study of the release of heavy metals from sediments by nitrilotriacetic acid (Zitko and Carson 1972), of the efect of humic acid on the toxicity of copper and of season of the year on the toxicity of zinc to juvenile Atlantic salmon (Zitko et al. 1973; Zitko and Carson 1977), work on thallium (Zitko et  al. 1975), on toxicity of pyrethroids to salmon (Zitko et al. 1977), and many other interesting projects, not mentioned here because of space limitations. Little can be done about chemicals that are already in the environment, but one should avoid surprises by unexpected presence of potentially risky chemicals in various materials. One such surprise was nonylphenol, present as a component of the pesticide aminocarb used in forest spraying in New Brunswick. It is more toxic to juvenile Atlantic salmon than the pesticide (McLeese et  al. 1980). Materials used in aquaculture require attention, Hexabromocyclododecane was found in expanded polystyrene beads from loats (Zitko 1993), 10,10′-oxybisphenoxarsine in plastic liners, decabromodiphenyl ether in iberglass of ish tanks (Zitko 1999), and long chain alkyl phosphates in the plastic coating of lobster traps (Zitko 2001a). An unintentional formation of irritants by faulty plumbing and poor laboratory techniques was detected in a histological laboratory (Zitko 2001b). For all these years, the Bulletin of Environmental Contamination and Toxicology was an excellent medium for sharing information. Unfortunately, environmental chemistry at the Biological Station attracted little attention in ‘A Century of Maritime Science’ (Hubbard et al. 2016). Hubbard J , DJ Wildish, RL Stephenson (eds) ( 2016 ) A century of maritime science . University of Toronto Press, Toronto, p 477 McLeese DW , Zitko V , Metcalfe CD , Sergeant DB ( 1980 ) Lethality of Aminocarb and of the components of the Aminocarb formulation to juvenile Atlantic salmon, marine invertebrates and a freshwater clam . Chemosphere 9 : 79 - 82 Roots O , Zitko V , Kiviranta H , Rantakokko P , Ruokojärvi P ( 2009 ) Concentrations and proiles of brominated diphenyl ethers (BDEs) in Baltic and Atlantic herring . Okeanologia 51 : 515 - 523 Zitko V ( 1970a ) Organic compounds in the Mactaquac impoundment . Fish Res Board Can MS Rep 1040:31 Zitko V ( 1970b ) Determination of residual fuel oil contamination of aquatic animals . Bull Environ Contam Toxicol 5 : 559 - 564 Zitko V ( 1970c ) Polychlorinated biphenyls (PCB) solubilized in water by nonionic surfactants for studies of toxicity to aquatic animals . Bull Environ Contam Toxicol 5 : 279 - 285 Zitko V ( 1971a ) Removal of protein-bound methyl mercury . Fish Res Board Can MS Rep 1131:11 Zitko V ( 1971b ) Polychlorinated biphenyls and organochlorine pesticides in some freshwater and marine ishes . Bull Environ Contam Toxicol 6 : 464 - 470 Zitko V ( 1974 ) Conirmation of chlorinated parains by dechlorina - tion . J Ass Of Anal Chem 57 : 1253 - 1259 Zitko V ( 1977 ) The accumulation of polybrominated biphenyls by ish . Bull Environ Contam Toxicol 17 : 285 - 292 Zitko V ( 1978 ) Nonachlor and chlordane in aquatic fauna . Chemosphere 7 : 3 - 7 Zitko V ( 1980a ) PCBs and other organochlorine copmpounds in sharks and tunas International Council for the Exploration of the Sea , C.M. 1980 /E:21, Marine Environmental Quality Committee Zitko V ( 1980b ) The uptake and excretion of mirex and Dechloranes by juvenile Atlantic salmon . Chemosphere 9 : 73 - 78 Zitko V ( 1980c ) Chlorinated parains . In: Hutzinger O (ed) The handbook of environmental chemistry . Part A , vol 3 . Springer, Heidelberg, pp 149 - 156 Zitko V ( 1983 ) “ Shorthand” numbering of chlorobiphenyls . Chemosphere 12 : 835 - 836 Zitko V ( 1993 ) Expanded polystyrene as a source of contaminants . Mar Pollut Bull 26 : 584 - 585 Zitko V ( 1999 ) Qualitative determination of 10,10′-oxybisphenoxarsine and decabromodiphenyl ether in plastics . Chemosphere 38 : 629 - 632 Zitko V ( 2001a ) A source of alkyl/aryl phosphates in the marine environment . Originally published in preprint .chemweb/chemistry, no longer available, can be obtained from author Zitko V ( 2001b ) Peroxides in Histoclear. Originally published in preprint .chemweb/chemistry, no longer available, can be obtained from author Zitko V , Carson WV ( 1969a ) Analysis of the eluent from the Domtar Wood Preserving Plant at Newcastle , N.B. Fish Res Board Can MS Rep 1024:14 Zitko V , Carson WV ( 1969b ) Acid pollution of the South Little River , N.B. Fish Res Board Can MS Rep 1041:24 Zitko V , Carson WV ( 1972 ) Release of heavy metals from sediments by nitrilotriacetic acid (NTA) . Chemosphere 3: 113 - 118 Zitko V , Carson WG ( 1977a ) Uptake and excretion of chlorinated diphenyl ethers and brominated toluenes by ish . Chemosphere 6 : 291 - 301 Zitko V , Carson WG ( 1977b ) A comparison of the uptake of PCB's and isopropyl-PCB's (Chloralkylene 12) by ish . Chemosphere 6 : 133 - 140 Zitko V , Carson WG ( 1977c ) Seasonal and developmental variation in the lethality of zinc to juvenile Atlantic salmon . J Fish Res Board Canada 34 : 129 - 142 Zitko V , Hutzinger O ( 1972 ) Sources, levels, and toxicological signiicance of PCB in hatchery-reared Atlantic salmon . Preprints of papers presented at 16th National Meeting, ACS Division of water, air and waste chemistry , New York, New York August 21 - September 1, 1972 , p 157 - 160 Zitko V , Hutzinger O ( 1976 ) Uptake of chloro- and bromobiphenyls, hexachloro- and hexabromobenzene by ish . Bull Environ Con - tam Toxicol 16 : 665 - 673 Zitko V , Aiken DE , Tibbo SN , KWT Besch, Anderson JM (1970a) Toxicity of yellow phosphorus to herring (Clupea harengus), Atlantic salmon (Salmo salar), lobster (Homarus americanus), and beach lea ( Gammarus oceanicus) . J Fish Res Board Can 27 : 21 - 29 Zitko V , Carson WG , BJ Finlayson (1970b) The inhibition of ish brain acetylcholinesterase activity by fenitrothion , Bay 77488 , and Dylox, and by the 1969 aerial spraying of fenitrothion in New Brunswick . Fish Res Board Can MS Rep 1108:11 Zitko V , Finlayson BJ , Wildish DJ , Anderson JM , Kohler AC ( 1971 ) Methyl mercury in freshwater and marine ishes in New Brun - swick, in the Bay of Fundy, and on the Nova Scotia banks . J Fish Res Board Can 28 : 1285 - 1291 Zitko V , Hutzinger O , Jamieson WD , PMK. Choi ( 1972 ) Polychlorinated terphenyls in the environment . Bull Environ Contam Toxicol 7 : 200 - 201 Zitko V , Carson WV , Carson WG ( 1973 ) Prediction of incipient lethal levels of copper to juvenile Atlantic salmon in the presence of humic acid by cupric electrode . Bull Environ Contam Toxicol 10 : 265 - 271 Zitko V , Carson WV , Carson WG ( 1975 ) Thallium: occurrence in the environment and toxicity to ish . Bull Environ Contam Toxicol 13 : 23 - 30 Zitko V , Carson WG , Metcalfe CD ( 1977 ) Toxicity of pyrethroids to juvenile Atlantic salmon . Bull Environ Contam Toxicol 18 : 35 - 41


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Vladimir Zitko. Reminiscence of Forty Years of Environmental Chemistry, Bulletin of Environmental Contamination and Toxicology, 2016, 749-751, DOI: 10.1007/s00128-016-1971-8