Picloram Herbicide A Technical Bibliography of Non-Target Effects Compiled by: Milo Mihajlovich, RPF Incremental Forest Technologies Ltd. Foreword The following compilation into one sourcebook of an extensive collection of abstracts on the herbicide picloram is intended to provide users of this herbicide ready access to the breadth and evolution of scientific understanding of this herbicide. Deliberate effects – for example, efficacy were not included – as the sourcebook is intended more to assist in understanding the likelihood and type of non-target effects associated with using this herbicide. A literature search of 15 databases resulted in a total of literally hundreds of references. These were sorted into 13 generalized categories to ease access and allow users of the bibliography to target specific concerns quickly and easily. The bibliography reflects the breadth and depth of understanding picloram from the perspective of refereed journals and without input from the compiler. The bibliography is designed as an information access tool, not as a stand-alone reference. Users are urged to identify literature of interest using the abstracts in the guide then to seek out the original publication(s) to more clearly understand the results and implications of the research. Abstracts from differing sources often varied slightly in extent and content. The compiler attempted to select the abstract, which provided the most information about both outcomes and methodologies. Where abstracts were not given none was prepared and the title alone was included in the bibliography. The literature search for compiling this bibliography was completed on February 2001. The thirteen categories of references were not used as exclusive sets – where an abstract suggested the article was cogent to several categories the attempt was made to include it in all appropriate categories. Milo Mihajlovich, RPF Incremental Forest Technologies Ltd. Edmonton, AB July, 2001 Acknowledgement and Thanks Preparation of this bibliography would not have been possible without the hard work and valuable combination of interest and skills of Ms. Valerie Sowiak. Her efforts and contribution to this bibliography are greatly appreciated. Table of Contents Bibliography of References for Non-target Field and Laboratory Reports of Picloram Herbicide Subject Page ANALYTICAL METHODOLOGY ............................................................................... 1 AQUATIC INVERTEBRATES.................................................................................... 23 ARTHROPOD TOXICITY........................................................................................... 28 BIODIVERSITY ........................................................................................................... 30 ENVIRONMENTAL FATE - PLANTS ....................................................................... 37 ENVIRONMENTAL FATE - SOILS ........................................................................... 45 ENVIRONMENTAL FATE - WATER ........................................................................ 76 FISH & AMPHIBIANS.................................................................................................93 HUMAN TOXICOLOGY............................................................................................. 99 MAMMALIAN TOXICOLOGY................................................................................ 106 AVIAN TOXICOLOGY ............................................................................................. 115 NON-TARGET PLANTS AND RECROPPING........................................................ 118 SOIL MICROBIOTA..................................................................................................131 ii Picloram Analytical Methodology ANALYTICAL METHODOLOGY Abramova, K.A., T.D. Panasyuk, and E.A. Kalinina. 1973. Determination of Tordon 22-K in soil and plants by a biological method. Khimiya v Sel'skom Khozyaistve. Vol. 11: 298-300. Russian Tordon 22-K picloram-potassium 24.9% was applied at 0.0036-0.0327 mg/kg to a 2:2:1 mixture of peat + soil + sand, in which French beans were sown as bioassay plants, in the glasshouse. The surface area of whole leaves was taken as a quantitative assessment of picloram residues in the soil. The sensitivity of the method was 0.003-0.004 mg/kg. Residues in the soil of 0.1 mg/kg reduced grain yields of wheat by 20% while 0.2 mg/kg almost entirely prevented grain formation. Residues in wheat straw from plants grown in soil containing 0.2-0.4 mg picloram/kg were determined by macerating plant tissues, mixing them in soil and leaving for 1-60 days before sowing French beans as bioassay plants; residues in the straw after 20 days in the soil averaged 5.47 mg/kg for the low application and 12.28 mg/kg for the high application. Agriculture Canada, Research Station, Kentville. 1976. Research Branch Report 1975, pp. 17-30. P. 25. Picloram residues. The potassium salt of picloram (Tordon 22K) at 4.48 kg/ha (2 p.p.m.) was soil-incorporated to a depth of 15 cm. Analysis of the soil 18, 63, 145, 337, 504, 690 and 843 days later showed the presence of picloram at 1.86, 1.78, 1.32, 0.7, 0.28, 0.12 and 0.02 p.p.m., respectively. Soil containing 1.32 p.p.m. picloram inhibited the growth of carrots, parsnips, potatoes, table beets and rutabagas sown in the glasshouse. One year after the application of picloram, the growth of sweet corn and oats was reduced by about 20% while beans (Phaseolus sp.), parsnips and Swiss chard (Beta vulgaris var. cicla) failed to grow at all. Picloram residues 1055 days after application were 2.5 parts per billion (109) as determined by a bioassay using bean.P. 25. Test for picloram. A rapid, sensitive and specific fluorescence test for picloram was developed. Sulphuric acid 36 N solution was added to the dry residue in quartz tubes or on a white porcelain plate. Under short wavelength UV radiation, yellow fluorescence was observed. The test can also be carried out using glass test tubes and long wavelength UV radiation but this method is not so sensitive. Agriculture Canada, Research Station, Regina. 1976. Research Branch Report 1975, pp. 265-272. P. 268. Herbicide behaviour in the environment. Results of investigations into the fate of herbicides in the environment are reported. The persistence of atrazine in Brown soils appeared to be related to Ca content and pH of the soil. The order of leachability of 3 uracil herbicides in a range of soil types was bromacil > terbacil > lenacil. Residue levels of 2,4-D of 0.002 and 0.017 mu g/m3 were detected in the air above Regina in June and July. The rate of volatilization of 2,4-D isooctyl ester from Asquith sandy loam soil was high for the first 24 h, after which time volatilization was negligible. The degradation of C-2242 (chlortoluron) in steam-sterilized soil was negligible, 1 Picloram Analytical Methodology indicating that microbiological processes are important for the breakdown of this herbicide. Residues from spring applications of benazolin, benzoylprop, alachlor, nitrofen, profluralin and picloram were detectable the following October while asulam had disappeared. Benzoylprop-ethyl, alachlor, nitrofen and profluralin were detected only in the top 5 cm of soil whereas residues of benazolin, picloram and the acid derivative of benzoylprop were observed at lower depths. In a study of the persistence of 4 herbicides in irrigation water, simazine was the most persistent, followed by atrazine, monuron and bromacil. Albanis, T.A. and D.G. Hela. 1995. Multi-residue pesticide analysis in environmental water samples using solid-phase extraction discs and gas chromatography with flame thermionic and mass-selective detection. J. of Chromatography. 707: 283-292. A multi-residue analysis for 25 pesticides was developed as a rapid screening method for organic contaminants in river, lake and sea water samples. Gas chromatography with flame thermionic detection (GC-FTD) and mass selective detection (GC-MSD) using 2 different capillary columns, DB-1 and HP-5, were employed for the identification of 25 selected pesticides belonging to the triazines, organophosphorus compounds and substituted ureas, carbamates, anilides, anilines and amides. The extraction of various natural waters spiked with pesticide mixtures was effected with C18 Empore solid-phase extraction discs and filter-aid glass beads. The triazine compounds (atrazine, simazine, propazine, prometryne and cyanazine) were recovered from distilled and underground water samples at relative high levels (73.5-105%) compared with the river waters (39.9-80.5%), lake water (54.6-81.8%) and marine water (38.6-79.9%). The organophosphorus compounds studied (monocrotophos, terbufos, diazinon, methyl parathion, ethyl parathion, malathion and ethion) were also recovered from distilled and underground water samples at relatively high levels (62.4-118%) compared with river waters (27.3-98.9%), lake water (41.0-85.2%) and marine water (33.4-81.3%). The substituted ureas (monuron, diuron and linuron), substituted anilines and anilides (trifluralin, propanil, propachlor and alachor), carbamates (EPTC and carbofuran) and other compounds (molinate, picloram, captan and MCPA isooctyl ester) were recovered at the same level as triazines. Confirmation of pesticide identity was performed by using GC-MS in the selected-ion monitoring mode. Baur, J.R. 1980. Release characteristics of starch xanthide herbicide formulations. Journal of Environmental Quality. 9: 379-382. A laboratory procedure was