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7/14/2009 5:02:32 PM
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UCREFRP
UCREFRP Catalog Number
7942
Author
Schmitt, C. J., et al.
Title
National Pesticide Monitoring Program
USFW Year
1983.
USFW - Doc Type
Organochlorine Residues in Freshwater Fish, 1976-79.
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5 <br />pounds were eluted with 30 mL of 4% ethyl acetate in <br />benzene. These eluates were concentrated and made ready <br />for GLC analysis along with Florisil eluate B. Aliquots of <br />1 µL were injected into a Packard 805 gas chromatograph <br />equipped with electron capture detectors. The glass column <br />(1.8 m x 4 mm i.d.) was packed with 1.5% OV-17 + <br />2.0% OV-210 on 100/120 Gas Chrom-Q. Temperatures <br />were as follows: column, 200° C; injector, 225° C; and de- <br />tector, 300° C. <br />Fractions giving chlordane response were analyzed on <br />a column (1.8 m x 4 mm i.d.) containing 3% SE-30 on <br />100/120 Gas Chrom-Q at 180° C to resolve cis- and trans- <br />chlordane from trans- non achlor. <br />The 1978-79 cross-check analyses were done at the Great <br />Lakes Fishery Laboratory, FWS, Ann Arbor, Michigan. <br />The analytical procedures used there were described by <br />Snyder and Reinert (1971) and Hesselberg and Nicholson <br />(1981). <br />Data Handling and Statistical Analyses <br />Improved analytical methods freed the residue values <br />determined for the collection years 1976 through 1979 from <br />the intercompound interferences reported for earlier NPMP <br />organochlorine analyses (Schmitt et al. 1981). The present <br />data were therefore amenable to more rigorous statistical <br />testing than were those for previous years. We analyzed <br />transformed values of percent lipid, wet-weight residues, <br />and lipid-weight residues by analysis of variance (ANOVA), <br />using the mixed nested-crossed model <br />Y4ki = µ + Li + Pi + LPij + Sk(LP) + Ei,kl <br />where Yi;kl = transformed value from location i, collection <br />period j, species k, and sample l;µ = the grand mean; <br />Li = random location effect; P, = fixed collection-period <br />effect; LPij = location-collection period interaction; Sk <br />(LP) = random effect of species within each location and <br />collection period; and Eijkl = error (among samples of the <br />same species). The rationale for using this model to test for <br />collection-period differences and the details of the overall <br />testing procedures were described by Schmitt (1981). <br />We used the Statistical Analysis System (SAS Institute, <br />Inc. 1979), available through the University of Mis- <br />souri-Columbia computer system (Amdahl 470 V7), for all <br />data handling and statistical analyses. For trend analyses, <br />the following descriptive statistics were computed for each <br />compound, by collection period: mean (after appropriate <br />transformation), minimum and maximum concentration, <br />and percentage of stations at which each compound was <br />detected. Least-squares means (SAS Institute, Inc. 1979), <br />which are adjusted for the number of observations per cell, <br />were examined throughout. Percent lipid values were nor- <br />malized by using the angular transformation (Schmitt <br />1981). Lipid-weight residue concentrations were computed, <br />and both lipid-weight and wet-weight concentrations were <br />normalized by applying the (log,„ [residue concentration + <br />1.0]) transformation before computation of means and <br />further statistical analyses. Schmitt et al. (1981) discussed <br />the applicability of these procedures to residue-monitoring <br />data. In addition to descriptive statistics, we computed <br />annual matrices of product-moment correlation coefficients <br />to illustrate trends in the co-occurrence of compounds. <br />To examine more thoroughly for temporal trends, we re- <br />analyzed some NPMP results from 1974 (Schmitt et al. <br />1981). After recomputing the ANOVA for data from 1974 <br />through 1979, we analyzed for differences among collec- <br />tion periods, using the sum-of-squares simultaneous test pro- <br />cedure to compare means (Sokal and Rohlf 1969). We then <br />used analysis of covariance (Snedecor and Cochran 1967) <br />to examine the significance and direction of the observed <br />changes in lipid-weight residues from 1974 through 1979. <br />The level of significance used in all statistical tests was <br />P s 0.05. <br />We used several statistical techniques to compare our re- <br />sults with corresponding values reported by the cross-check <br />laboratories. Summary statistics were computed for each <br />laboratory's results after the data were transformed (as <br />described), and percent occurrence was compared. For each <br />compound, the product-moment correlation coefficient (r) <br />between corresponding values was computed to give a <br />general indication of agreement. We also used linear regres- <br />sion (Snedecor and Cochran 1967) to test for overall agree- <br />ment, computing slope (b) and intercept (a) values for the <br />relationship y = a + bx, where y = cross-check value and <br />x = original CNFRL value. We then tested the coefficients <br />to determine whether the slopes (b) differed significantly <br />from 1.0 or the intercepts (a) differed from 0.0 (perfect <br />agreement between laboratories would yield relations in <br />which a = 0.0, b = 1.0, andv = 1.0). Overall differences <br />between laboratories were tested by using two-way ANOVA <br />for paired comparisons (Sokal and Rohlf 1969). <br />Results and Discussion <br />Characteristics and Limitations of the Data <br />Among the 112 active NPMP stations (Fig. 1), collections <br />were made at 106 (94%) in 1976-77 and at 108 (96%) in <br />1978-79; 102 stations (91 %) yielded data in both 1976-77 <br />and 1978-79 (Table 2). This 102-station subset of data from <br />both periods contained 591 samples (95% of the 1976-79 <br />data). There were 78 stations (out of a possible 113) with <br />complete data from 1974 through 1979 that could be <br />analyzed for temporal trends; this subset contained 753 ob- <br />servations (Table 2). <br />As reported previously by Schmitt et al. (1981), the <br />species collected at the NPMP stations have varied from year <br />to year. A total of 58 taxa were sent to CNFRL for residue <br />determinations in 1976-79 and 71 taxa in 1970-74. Overall, <br />the five most frequently collected species changed little from
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