USGS

Open-File Report 93-371

Cross Sectional Concentration Data for Selected Organic Contaminants in River Waters near the Confluence of the Mississippi River and the Illinois, Missouri, and Ohio Rivers, June 1989 and May-June 1990

By Colleen E. Rostad, LaDonna M. Bishop, Wilfred E. Pereira, and Thomas J. Leiker

The PDF for the report is 481 kb


Table of Contents

Abstract

Introduction

Sample Collection, Preparation, and Analysis

Results

Literature Cited

Figures

Figure 1. Location of sampling cross-sections below the confluence of the M...

Tables

Table 1. Compounds for which samples were analyzed and their applications.

Table 2. Herbicide data for the Mississippi River at St. Louis, Missouri, J...

Table 3. Herbicide data for the Mississippi River below Hickman, Kentucky, ...

Table 4. Industrial organic-contaminant data for the Mississippi River at S...

Table 5. Industrial organic-contaminant data for the Mississippi River belo...

Table 6. Industrial organic-contaminant data for the Mississippi River near...

Table 7. Industrial organic-contaminant data for the Mississippi River for ...

Table 8. Industrial organic-contaminant data for the Mississippi River at W...

Table 9. Industrial organic-contaminant data for the Mississippi River near...

Table 10. Industrial organic-contaminant data for the Mississippi River abo...

Table 11. Industrial organic-contaminant data for the Mississippi River at ...

Table 12. Average, minimum, and maximum uncertainties of replicate analyse...

Table 13. Average, minimum, and maximum uncertainties for replicate analyse...


Abstract

Water samples were collected upstream and downstream from the confluence of the Ohio River and Mississippi River to study mixing of the river waters. Samples collected in June 1989 on the Mississippi River were analyzed for alachlor, atrazine, 2-chloro-2',6'-diethylacetanilide, cyanazine, desethyl-atrazine, desisopropylatrazine, 2,6-diethylaniline, 2-hydroxy-2',6'-diethylacetanilide, metolachlor, simazine, trimethyltriazinetrione, tris(2-chloroethyl) phosphate, and tris(chloroisopropyl) phosphate. Samples collected upstream and downstream from the confluence of the Ohio River and Mississippi River in May-June 1990 were analyzed for trimethyltriazinetrione, tris(2-chloroethyl) phosphate, and tris(chloroisopropyl) phosphate. Concentration data for six to fifteen locations across the rivers are presented in tabular form for two sites in 1989 and six sites in 1990.

Introduction

A knowledge of how rivers mix at and downstream from their confluence provides a basis for prediction of pollutant transport and dilution; such information can be gained by assessment of the distribution of contaminants in the river water. The U.S. Geological Survey conducted a study of pollutant transport in the Mississippi River from St. Louis, Missouri to New Orleans, Louisiana from July 1987 to June 1990.

The sampling protocol for the Mississippi River study from July 1987 to June 1989 consisted of collecting composite samples along cross-sections of the river and selected tributaries. The sampling protocol was expanded in June 1989 to include discrete samples collected at verticals along a cross-section. Water samples were collected at two sites—one site downriver from the Upper Mississippi-Missouri-Illinois River confluence near St. Louis, Missouri, and one site downriver from the Upper Mississippi-Ohio River confluence near Hickman, Kentucky.

In May-June 1990 the study focused on the Upper Mississippi-Ohio River confluence and was expanded to seven sampling sites. The purpose of this phase of the study was to compare the transverse mixing that occurs along a straight reach of the river with the mixing that occurs along a curved reach of river. The straight reach started at the sampling site at Wickliffe, Kentucky (5 kilometers (km) downriver from the confluence), and ended 23 km downriver at the sampling site near Columbus, Kentucky. The curved reach started at the sampling site above New Madrid, Missouri (88 km downriver from the confluence), and ended 83 km downriver at the sampling site at Point Pleasant, Missouri. The Point Pleasant, Missouri, sample was lost, however. The final sampling site was at Caruthersville, Missouri (171 km downriver from the confluence), and was presumed to be a location where the Upper Mississippi and Ohio Rivers had completely mixed. Additionally, two upriver sites were sampled to determine initial concentrations of industrial organic contaminants prior to mixing: Cairo, Illinois 12 km upriver from the confluence on the Upper Mississippi River, and Olmsted, Illinois 27 km upriver from the confluence on the Ohio River. The samples collected during this phase of the study were analyzed for three industrial organic contaminants. Data in this report include results of analyses from June 1989 to July 1990.

Purpose and Scope

This report presents (1) a brief description of the methods of sample collection, preparation, and analysis, and (2) the results of analyses for the samples collected in June 1989 and May-June 1990. The compounds for which the samples were analyzed and their typical applications are listed in table 1.

Table 1. Compounds for which samples were analyzed and their applications.

Compound Application Reference
Herbicides
alachlor Herbicide used on corn and soybean crops to control annual grasses, broadleaf weeds and nutsedge Humburg and others, 1989
atrazine Selective herbicide used on corn and sorghum crops to control broadleaf and grassy weeds Humburg and others, 1989
2-chloro-2',6'- diethylacetanilide Degradation product of alachlor Aizawa, 1982
cyanazine Herbicide used in controlling annual grasses and broadleaf weeds for corn, grain sorghum, and cotton Humburg and others, 1989
desethylatrazine Degradation product of atrazine Aizawa, 1982
desisopropylatrazine Degradation product of atrazine Aizawa, 1982
2,6-diethylaniline A starting material for the manufacturing of alachlor
2-hydroxy-2',6'- diethylacetanilide Degradation product of alachlor Aizawa, 1982
metolachlor Herbicide used in controlling annual grasses, and certain broadleaf weeds on corn and cotton crops Humburg and others, 1989
simazine Widely used herbicide for corn crops to control broadleaf and grass weeds Humburg and others, 1989
Industrial organic contaminants
trimethyltriazinetrione unknown
tris(2-chloroethyl) phosphate A flame retardant and plasticizer Hawley, 1981
tris(chloroisopropyl) phosphate A flame retardant Hawley, 1981

Acknowledgments

This study could not have been completed without the help of the following people. Wayne Simoneaux was instrumental in holding the research vessel within about 3-5 meters of each sampling location under difficult weather conditions and boat traffic, and Wilton Delaune operated the winch for the May-June 1990 sampling. The assistance during sampling of Terry Brinton, Pat Brown, Deborah Martin, Robert Meade, John Moody, Terry Rees, James Seeley, Herbert Stevens, and Howard Taylor was appreciated.

Sample Collection, Preparation, and Analysis

Water samples were collected on the Mississippi River at St. Louis, Missouri, on June 9, 1989 and near Hickman, Kentucky, on June 13, 1989. In May-June 1990 samples were collected upriver and downriver from the confluence of the Mississippi River and Ohio River. These sites are shown in figure 1. The samples were collected in a Teflon bag sampler using a Teflon nozzle; this sampler was lowered to the river bottom and raised back to the surface at a constant rate in order to obtain a depth-integrated sample. Further details of this procedure, the exact location of sampling sites, and associated hydrologic data are described elsewhere by Moody and Meade (1993).


Location of sampling cross-sections below the confluence of the Mississippi and Ohio Rivers.

Figure 1. Location of sampling cross-sections below the confluence of the Mississippi and Ohio Rivers. The number after the site name is the river mile [modified from Moody and Meade, 1993).


A 1-liter (L) aliquot was collected for each depth-integrated sample, preserved with five drops of chloroform, and refrigerated until extraction. These samples were extracted using the following liquid-liquid extraction technique. Samples were filtered through a 0.45-micron glass-fiber filter and adjusted to pH 8.5 with 10 percent potassium hydroxide. Fifteen grams of sodium chloride and an internal standard were added to the samples, which were subsequently extracted three times with methylene chloride using 75-, 50-, and 50-mL volumes successively for the 1990 samples, and 100-, 50-, and 50-mL volumes for the 1989 samples. The combined methylene chloride extracts were dried over anhydrous sodium sulfate and concentrated in a Kuderna-Danish apparatus to an approximate volume of 5 mL. Four drops of benzene was added, and the extract was further concentrated to a volume of 100 microliters under a slow stream of dry nitrogen gas. The extracts for June 1989 and May-June 1990 samples were then analyzed for trimethyltriazinetrione, tris(2-chloroethyl)phosphate, and tris(chloroisopropyl)-phosphate by gas chromatography/positive chemical ionization/tandem mass spectrometry. The extracts for June 1989 samples were also analyzed for selected herbicides and their degradation products by using the same method (Rostad and others, 1989).

Results

The results of analyses for the June 1989 samples and the mean concentration for the replicate analyses are listed in tables 2-5. Along with the mean concentration, the uncertainty or error, which is one half the range (Taylor, 1982) in the data, is also shown. The results of analyses for the May-June 1990 samples together with the mean and uncertainty of replicate analyses are presented in tables 6-11. Note that locations from left edge of water are as viewed facing downstream.

Table 2. Herbicide data for the Mississippi River at St. Louis, Missouri, June 9, 1989. Total river width was 508 meters.

[ng/L, nanograms per liter; ±, uncertainty of duplicate analyses; nd, not detected]

Concentration (ng/L) at points from left edge of water, in meters
Compound 45 78 112 139 177 233 279 323 384 459
alachlor 740 720±9 730 710 660 570 520 470 600 1,600
atrazine 1,700 1390±30 1,800 1,400 1,500 1,600 1,300 1,200 1,100 1,100
2-chloro-2',6'-diethylacetanilide 19 20±4 20 22 13 18 13 15 110 630
cyanazine 900 880±70 1,000 1,000 1,000 1,200 990 1,100 1,000 980
desethylatrazine 130 160±30 130 140 100 88 100 97 85 80
desisopropylatrazine 90 100±9 62 81 nd 21 52 nd 8.1 2.3
2,6-diethylaniline 3.5 3.4±0.2 2 2.4 2.3 1.5 1.0 4.6 90 400
2-hydroxy-2',6'- diethylacetanilide 44 41±8 36 23 15 11 20 6.2 11 18
metolachlor 970 930±16 980 920 970 910 920 890 850 840
simazine 43.6 65±19 45 59 60 37 42 79 43 33

Table 3. Herbicide data for the Mississippi River below Hickman, Kentucky, June 13, 1989. Total river width was 1135 meters.

[ng/L, nanograms per liter; ±, uncertainty for duplicate analyses]

Concentration (ng/L) at points from left edge of water, in meters
Compound 64 173 288 399 518 629 741 862 966 1081
alachlor 390 430 440 420 500 560 670 650 680±20 690±10
atrazine 1,400 1,500 1,500 1,200 1,600 1,600 1,600 1,600 1300±10 1600±70
2-chloro-2',6'-diethylacetanilide 11 8.9 11 14 20 26 49 50 49±2 54±5
cyanazine 710 780 700 670 780 850 980 900 830±80 1000±20
desethylatrazine 200 220 200 200 240 230 260 170 200±5 180±8
desisopropylatrazine 53 28 71 54 96 46 80 87 73±22 72±1
2,6-diethylaniline 0.8 1.2 1.8 2.9 7 5.8 7.5 15 13±1 13±1
2-hydroxy-2',6'-diethylacetanilide 5.7 3.8 1.9 5.6 7.3 8.7 16 11 25±6 9.8±0.7
metolachlor 800 840 860 810 900 970 1,100 970 940±2 960±7
simazine 150 170 170 170 210 170 190 110 120±3 98±10

Table 4. Industrial organic-contaminant data for the Mississippi River at St. Louis, Missouri, June 9, 1989. Total river width was 508 meters.

[ng/L, nanograms per liter; ±, uncertainty for duplicate analyses; nd, not detected]

Concentration (ng/L) at points from left edge of water, in meters
Compound 45 78 112 139 177 233 279 323 384 459
trimethyltriazinetrione 0.7 1.2±0.1 nd 0.9 nd nd nd 1.4 0 0.5
tris(2-chloroethyl)phosphate 120 96±23 110 97 90 69 67 45 31 19
tris(chloroisopropyl)phosphate 890 820±130 790 720 660 430 340 280 160 39

Table 5. Industrial organic-contaminant data for the Mississippi River below Hickman, Kentucky, June 13, 1989. Total river width was 1,135 meters.

[ng/L, nanograms per liter; ±, uncertainty for duplicate analyses]

Concentration (ng/L) at points from left edge of water, in meters
Compound 64 173 288 399 518 629 741 862 966 1081
trimethyltriazinetrione 60 54 58 65 86 65 46 31 18±0 0.7
tris(2-chloroethyl)phosphate 14 13 15 18 29 32 48 52 56±0.6 59±2
tris(chloroisopropyl)phosphate 40 53 72 65 93 140 250 270 470±140 300±7

Table 6. Industrial organic-contaminant data for the Mississippi River near Cairo, Illinois, May 31, 1990. Total river width is 696 meters.

[ng/L, nanograms per liter; ±, uncertainty for duplicate analyses]

Concentration (ng/L) at points from left edge of water, in meters
Compound 161 280 418 464 509 614
trimethyltriazinetrione 0.4±0.3 0.8±0.6 0.7±0.5 1.7±1.1 3.2±4.5 2.5±1.9
tris(2-chloroethyl)phosphate 93±13 85±7 93±17 98±15 70±23 110±8
tris(chloroisopropyl)phosphate 98±18 88±14 94±18 97±17 89±6 110±18

Table 7. Industrial organic-contaminant data for the Mississippi River for the Ohio River at Olmsted, Illinois, May 31, 1990. Total river width was 1098 meters.

[ng/L, nanograms per liter;±, uncertainty for triplicate analyses]

Concentration (ng/L) at points from left edge of water, in meters
Compound 74 141 199 248 347 416 491 553 612 685 758 821 879 941 1005
trimethyltriazinetrione 37±5 39±6 38±5 47±5 25±5 35±5 41±11 60±13 44±8 28±7 40±9 39±6 53±7 34±7 30±12
tris(2-chloroethyl)phosphate 38±53 52±1 22±9 21±8 18±7 23±6 25±5 20±8 23±5 20±8 24±2 24±8 26±6 20±1 27±9
tris(chloroisopropyl)phosphate 19±6 41±3 23±4 29±3 19±3 24±2 21±3 21±5 22±4 22±1 22±9 34±4 25±1 20±4 21±5

Table 8. Industrial organic-contaminant data for the Mississippi River at Wickliffe, Kentucky, June 1, 1990. Total river width was 827 meters.

[ng/L, nanograms per liter; ±, uncertainty for triplicate analyses]

Concentration (ng/L) at points from left edge of water, in meters
Compound 65 103 159 199 264 306 349 412 459 501 552 603 645 697 750
trimethyltriazinetrione 55±12 44±9 40±7 36±6 21±5 0.2±0 8.9±3.3 4.6±2.3 0.6±0.3 0.8±0.5 0.8±0.5 0.3±0.2 1.5±1.1 0.5±0.3 0.6±0.3
tris(2-chloroethyl) phosphate 22±8 31±12 28±2 34±3 71±9 53±11 86±9 99±9 170±14 96±6 110±10 110±8 99±30 99±10 110±13
tris(chloroisopropyl)phosphate 27±8 29±7 31±5 29±5 68±16 55±10 83±15 97±13 170±19 97±12 110±16 120±12 120±9 120±18 110±31

Table 9. Industrial organic-contaminant data for the Mississippi River near Columbus, Kentucky, June 1, 1990. Total river width was 912 meters.

[ng/L, nanograms per liter; ±, uncertainty for triplicate analyses]

Concentration (ng/L) at points from left edge of water, in meters
Compound 69 118 170 229 283 336 412 461 507 581 630 680 725 784 851
trimethyltriazinetrione 47±10 37±7 36±5 27±4 13±1 8.9±1.5 5.7±0.9 3.6±0.6 4.4±0.9 1.9±0.1 3±0.5 2.4±0.1 3.2±0.2 2.6±0.4 2.8±0
tris(2-chloroethyl) phosphate 200±16 55±8 68±9 140±11 84±6 94±5 104±6 94±4.2 100±4 100±12 110±12 110±9 100±3 120±14 100±6
tris(chloroisopropyl)phosphate 52±8 35±9 42±8 78±1 72±11 83±7 100±11 84±13 100±9 95±14 110±14 110±12 100±8 120±15 97±6

Table 10. Industrial organic-contaminant data for the Mississippi River above New Madrid, Missouri, June 2, 1990. Total river width was 1,060 meters.

[ng/L, nanograms per liter; ±, uncertainty for triplicate analyses]

Concentration (ng/L) at points from left edge of water, in meters
Compound 120 228 326 371 426 536 640 748 850 959
trimethyltriazinetrione 28±5 28±0.7 20±0.1 23±3 17±0.4 13±0.6 12.8±1 7±2 13±0.1 13±1.1
tris(2-chloroethyl) phosphate 100±9 100±12 97±15 80±12 100±13 100±10 93±1.9 95±4.2 120±5 140±5
tris(chloroisopropyl)phosphate 83±12.8 79±0.4 81±1.4 84±17 82±2.8 100±7 97±19 99±8.4 120±27 120±19

Table 11. Industrial organic-contaminant data for the Mississippi River at Caruthersville, Missouri, June 3, 1990. Total river width was 849 meters.

[ng/L, nanograms per liter; ±, uncertainty for triplicate analyses]

Concentration (ng/L) at points from left edge of water, in meters
Compound 95 179 257 344 432 518 589 655 738
trimethyltriazinetrione 28±1.6 19±1.7 23±9 14±2.5 19±19 18±3 5.5±5.4 16±4.5 16±1.2
tris(2chloroethyl) phosphate 63±3.3 59±3.4 95±9 53±7.7 81±25 61±1.3 60±6.1 68±7.6 87±6.3
tris(chloroisopropyl)phosphate 79±7.4 77±11 130±27 75±1.9 130±10 72±6.6 74±8.6 86±13 86±9.4

Variation in concentration values may result from inconsistencies in sample collection, extraction, and/or analytical (instrumentation) errors. Potential errors in the sampling procedure are described by Moody and Meade (1993). Extraction and recovery variability from the liquid-liquid extraction method are unknown unless duplicate samples were extracted for analysis, which were unavailable due to sample limitations. Analytical variation was determined as the uncertainty of replicate analyses. Average, minimum, and maximum values of the uncertainty expressed as a percentage of the mean concentration for replicate analyses are presented in tables 12-13. In table 13, the large uncertainty of some values is due to instrumental variability for the polar compound, trimethyltriazinetrione, which chromatographs poorly. Average values shown in tables 12-13 were determined from non-rounded values from previous tables.

Table 12. Average, minimum, and maximum uncertainties of replicate analyses as a percentage of the mean concentration for the herbicide data.

[n.d., not determined because of insufficient data]

Compound Average Minimum Maximum
Mississippi River at St. Louis, Missouri, June 9, 1989
alachlor 1.2 n.d. n.d.
atrazine 2.2 n.d. n.d.
2-chloro-2',6'-diethylacetanilide 18 n.d. n.d.
cyanazine 8.5 n.d. n.d.
desethylatrazine 19 n.d. n.d.
desisopropylatrazine 8.8 n.d n.d
2,6-diethylaniline 5.9 n.d n.d.
2-hydroxy-2',6'-diethylacetanilide 20 n.d. n.d.
metolachlor 1.7 n.d. n.d.
simazine 29 n.d. n.d.
Mississippi River below Hickman, Kentucky, June 13, 1989
alachlor 2.6 2.2 2.9
atrazine 2.6 0.8 4.4
2-chloro-2',6'-diethylacetanilide 6.7 4.7 8.7
cyanazine 5.5 1.9 9.1
desethylatrazine 3.5 2.6 4.5
desisopropylatrazine 16 1.5 29
2,6-diethylaniline 4.2 3.7 4.8
2-hydroxy-2',6'-diethylacetanilide 15 7.1 23
metolachlor 0.5 0.2 0.7
simazine 6.3 2.6 10

Table 13. Average, minimum, and maximum uncertainties for replicate analyses as a percentage of the mean concentration for the industrial organic-contaminant data.

[n.d., not determined because of insufficient data]

Compound Average Minimum Maximum
Mississippi River at St. Louis, Missouri, June 9, 1989
trimethyltriazinetrione 8.3 n.d. n.d.
tris(2-chloroethyl) phosphate 24 n.d. n.d.
tris(chloroisopropyl) phosphate 16 n.d. n.d.
Mississippi River below Hickman, Kentucky, June 13, 1989
trimethyltriazinetrione 1.8 0 3.5
tris(2-chloroethyl) phosphate 2.1 1.1 3.1
tris(chloroisopropyl) phosphate 16 2.3 29
Mississippi River near Cairo, Illinois, May 31, 1990
trimethyltriazinetrione 83 65 140
tris(2-chloroethyl) phosphate 16 7.5 32
tris(chloroisopropyl) phosphate 16 7 19
Ohio River at Olmsted, Illinois, May 31, 1990
trimethyltriazinetrione 19 11 38
tris(2-chloroethyl) phosphate 34 2.1 140
tris(chloroisopropyl) phosphate 17 4.4 41
Mississippi River at Wickliffe, Kentucky, June 1, 1990
trimethyltriazinetrione 40 0 73
tris(2-chloroethyl) phosphate 15 5.9 38
tris(chloroisopropyl) phosphate 17 7.6 30
Mississippi River near Columbus, Kentucky, June 1, 1990
trimethyltriazinetrione 13 0 22
tris(2-chloroethyl) phosphate 8.1 2.9 14
tris(chloroisopropyl) phosphate 13 6 25
Mississippi River above New Madrid, Missouri, June 2, 1990
trimethyltriazinetrione 8.8 0.5 29
tris(2-chloroethyl) phosphate 8.6 1 15
tris(chloroisopropyl) phosphate 11 0.5 22
Mississippi River at Caruthersville, Missouri, June 3, 1990
trimethyltriazinetrione 36 5.6 100
tris(2-chloroethyl) phosphate 11 2.1 32
tris(chloroisopropyl) phosphate 11 2.5 21

Literature Cited

Aizawa, Hiroyasu, 1982, Metabolic Maps of Pesticides: New York, Academic Press, 219 p.

Hawley, G.G., 1981, The Condensed Chemical Dictionary, Tenth Edition: New York, Van Nostrand Reinhold Company Inc., 1135 p.

Humburg, N.E., Colby, S. R., Hill, E.R., Kitchen, L.M., Lym, R.G., McAvoy, W.J., Prasad, Raj, 1989, Herbicide Handbook of the Weed Science Society of America, Sixth Edition: Champaign, Illinois, Weed Science Society of America, 301 p.

Moody, J.A., and Meade, R.H., 1993, Hydrological and sedimentological data collected during four cruises at high water on the Mississippi River and some of its tributaries, March 1989-June 1990: U.S. Geological Survey Open-File Report 92-651, 227 p.

Rostad, C.E., Pereira, W.E., and Leiker, T.J., 1989, Determination of herbicides and their degradation products in surface waters by gas chromatography/positive chemical ionization/tandem mass spectrometry: Biomedical and Environmental Mass Spectrometry, vol. 18, p. 820-827.

Taylor, J.R., 1982, An introduction to error analysis: The study of uncertainties in physical measurements: Mill Valley, California, University Science Books, Oxford University Press, 270 p.

Document Accessibility: Adobe Systems Incorporated has information about PDFs and the visually impaired. This information provides tools to help make PDF files accessible. These tools convert Adobe PDF documents into HTML or ASCII text, which then can be read by a number of common screen-reading programs that synthesize text as audible speech. In addition, an accessible version of Acrobat Reader 6.0, which contains support for screen readers, is available. These tools and the accessible reader may be obtained free from Adobe at Adobe Access.


U.S. Department of the Interior, U.S. Geological Survey
Persistent URL:
Page Contact Information: Contact USGS
Last modified: Wednesday, December 07 2016, 07:29:26 PM
FirstGov button  Take Pride in America button