Published 1974

PESTICIDES IN SOIL AND WATER

PESTICIDES IN SOIL
AND WATER
Editorial Committee
W. D. GUENZI, editor

J. L. AHLRICHS

G.CHESTERS

M. E. BLOODWORTH

R.G.NASH

Managing Editor
RI(~HARD C.

DINAUER

Assistant Editors
MARGARET E. DAVIS
LINDA EISELE

Soil Science Society of America, Inc., publisher

Madison, Wisconsin USA
1974

The cover design is by Ruth C. Poulsen,

staff artist with the American Society of
Agronomy, Madison, Wis. The composition for the text pages was done by Mrs.
Linda Nelson on an IBM Selectric Composer using the Baskerville type font.

Copyright 1974 by the Soil Science Society of America, Inc.

ALL RIGHTS RESERV~D
No part of this book may be reproduced or utilized in any
form or by any means, electronic or mechanical, including
xerography, photocopying, microfilm, and recording, or by
any information storage and retrieval system, without
permission in writing from the publisher.

Second Printing 1981

Soil Science Society of America, Inc.
677 South Segoe Road, Madison, Wisconsin 53711 USA

Library of Congress Catalog Card Number: 74-76652

Printed in the United States of America

CONTENTS
Page
xiii
xv
xvii
xix

FOREWORD.
PREFACE
CONTRIBUTORS
CONVERSION FACTORS FOR ENGLISH AND METRIC UNITS

Introduction
VV AYNE D. GUENZI

Pesticide-Clay-Water Interactions
R. E. GREEN
I. Introduction.
II. Soil Clays as Adsorben ts .
III. Pesticides as Adsorbates .
A. Chemical Properties of Pesticides Relevant to Adsorption
on Clays.
B. Adsorption of Specific Types of Pesticides on Clay
Minerals .
C. Adsorption Mechanisms
1. Cationic Bonds
2. Anionic Bonds
3. Cation-Dipole and Coordination Bonds
4. Hydrogen Bonds .
5. Van Der Waals Attractions
IV. Water as a Solvent .
A. Properties of Water
B. Clay-Water Interactions
C. Pesticide-Water Interactions

12
18
18

21
23
25
27
28
28
29

30

33

LITERATURE CITED

3
5

Pesticide-Organic Matter Interactions

S. B. WEED and]. B. WEBER
I.
II.
III.
IV.
V.

Introduction .
Nature of Soil Organic Matter .
Nature of Pes ticide Molecules .
Methods of Study .
Mechanisms of Adsorption
A.. Cation Exchange
B. Hydrogen Bonding
C. Nonpolar van der Waals Force
D. Hydrophobic Bonding
E. Ligand Exchange
F. Reactions Involving Free Radicals
G. N onbiological Al teration
VI. Adsorption of Organic Pesticides
A. Cationic Compounds .
B. Basic Compounds
C. Acidic Compounds
D. Nonionic Pesticides

LITERATURE CITED

39
40

43
44
46
46
48
48
49
49
50
50
50
50
51
54

55
60

ConUn~

Movement of Pesticides in Soil

]. LETEY and W.]. FARMER
I. Introduction.
II. Diffusion
A. Theoretical Considerations .
B. Published Resul ts
1. Soil Water Content
2. Adsorption .
3. Bulk Density
4. Temperature
5. Fumigation.
C. General Conclusions .
III. Mass Flow
A. Theoretical Considerations .
B. Published Results
C. Conclusions
IV. Appendix A-List of Symbols .
V. Appendix B-Chemical Designations of Pesticides Mentioned
in Text.
LITERATURE CITED

67
67
67
70
70

74
76
76
77
78

80
80
86
92
92
93

94

Movement of Pesticides in Surface Water

M. G. MERKLE and R. W. BOVEY
I. Introduction.

II.
III.
IV.
V.

Occurrence of Pesticides in Surface Waters .

Factors which Affect the Loss of Pesticides into Surface Water
Significance of Pesticides in Surface Water .
Controlling the Movement of Pesticides
VI. Summary
LITERATURE CITED

99
99
101
104
104

105
106

Volatilization of Pesticides
w. D. GUENZI and W. E. BEARD
I. Introduction.

II. Application Losses .

III. Factors Controlling Volatilization from Soil
A. Physical and Chemical Properties of the Pesticide
B. Sorptive Characteristics of the Soil
C. Pesticide Concentration
D. Soil Water
E. Air Flow Rate .
F. Temperature
G. Diffusion.
IV. Measured '/olatilization Losses from Field Soils .
LITERATURE CITED .

107
107
109
110
112
113
113
116
117
117
118
120

Nonbiological Degradation of Pesticides

D. E. ARMSTRONG and]. G. KONRAD
I. Introduction.

II. Hydrolysis Reactions

A. Chloro-s-Triazine Herbicides

123
123

123

Contents

VB

126
128
128
129

B. Organophosphate Insecticides
C. Other Compounds
III. Photochemical Degradation
IV. Other Reactions
LITERATURE CITED

130

Degradation of Pesticides by Soil Microorganisms

D. D. KAUFMAN
I. Introduction.
II. Chlorinated Hydrocarbons
A. DDT, DDD, and Dicofol
B. Chlorobenzilate, Chloropropylate, and Methoxychlor
C. Cyc10dienes
D. Lindane .
III. Organophosphates .
IV. Pyrethroids .
V. Carbamates .
A. Methylcarbamates
B. Thiocarbamates
C. Dithiocarbamates
D. Phenylcarbamates
VI. Phenylamides
A. Carbanilates
B. Phenylureas
C. Acylanilides
D. Toluidines
E. Acetamides
VII. Phenoxyalkanoates.
VIII. s-Triazines
IX. Heavy Metal and Metalloids
A. Mercurials
B. Arsenicals
X. Miscellaneous
A. Aliphatic Acids.
B. Benomyl.
C. Benzoic Acids .
D. Carboxin.
E. Chlorani!.
F. Chloroneb
G. Dazom@i'
H. Dexon R
I. Dodine
J. Dipyridyls
K. Endothall
L. Nitrophenols
M. PCNB
N. PCP
O. Phthalimides
P. Pyrazon .
Q. Pyridines.
R. Uracils
XI. Pesticide Combinations .
XII. Summary
XIII. Appendix

133
135
135
138
139
142
143
147
147
148
150
152
153
154
158
158
159
161
162
163
168
169
170
171
172
172
172
173
174
174
174
174
175
175
175
176
176
177
177
177
178
178
178
179
179
180

LITERATURE CITED

185

Contents

VIll

Persistence of Pesticides in Soil

A. E. HILTBOLD
I. Introduction.
II. Order of Persistence Among Pesticide Classes and Compounds
III. Time Dependence of Pesticide Loss .
A. Time Independent Loss
1. History of Arsenic Accumulation in Soils .
2. Fate of Arsenic in Soils .
B. Time Dependent Loss
1. Microbiological Response-Lag and Enrichment
2. No Microbiological ,Response-Dependence on
Concentration
IV. Cultural Practices and Pesticide Persistence.
V. Appendix
LITERATURE CITED

10

203
204
205
205
205
208
209
209
211

215
218

220

Effects of Soil on the Biological Activity of Pesticides

J. B. WEBER and S. B. WEED

223
223
224
224
224
225
225
226
226

I. Introduction.
II. Nature and Classification of Pesticides
A. Ionizability
B. Water Solubility
C. Polarizability
D. Volatility
E. Formulations
F. Rate of Application .
G. Placement
III. Nature of Soil Particulate Matter
A. Clay Minerals
B. Organic Matter.
C. Metallic Hydrous Oxides
IV. Bioactivity of Adsorbed Organic Chemicals.
V. Bioactivity of Adsorbed Pesticides
A. Cationic Pesticides
B. Basic Pesticides.
C. Acidic Pesticides
D. Miscellaneous Ionic Pesticides
E. Chlorinated Hydrocarbons .
F. Organophosphates
G. Dinitroanilines .
H. Methylcarbamates and Carbanilates
I. Ureas, Anilides, and Amides
J. Volatile Pesticides
VI. Summary
VII. Acknowledgments .
VIII. Appendix
LITERATURE CITED

11

226

227
227

228
228
229
230
232
234
236
237

238
239
240
241

242
243
244
244
250

Plant Uptake of Insecticides, Fungicides, and Fumigants from Soils

RALPH G. NASH

I. In troduction .
II. Discussion
A. Insecticides
1. Chlorinated Hydrocarbons
2. Organophosphates.

257

258
258
258
265

Contents
3. Carbamates .
4. Arsenic
5. Lead .
B. Fungicides
C. Fumigan ts-N ematicides
D. General .
III. Appendix
LITERATURE CITED

12

265
266
266
266
267
267
269
307

Effects of Pesticides on Microorganisms in Soil and Water

J. F. PARR
I. Introduction.
II. Theoretical Considerations
III. Effects on Nitrification and Ammonification
A. Herbicides
1. Effects of Some Older Compounds .
2. Effects of Some N"ewer Compounds .
3. Differential Effects of Some Herbicides and Their
Degradation Products on Nitrifying Bacteria
4. Significance of the Inherent Nitrifying Capacity.
B. Insecticides
C. Fungicides and Fumigants .
1. Effects of Some Older Compounds .
2. Effects of Some Newer Compounds.
IV. Ecological and Pathological Effects of Fungicides and Fumigants
V. Effects of Pesticides on Soil Respiration
VI. Effect of Pesticides on Symbiotic Nitrogen Fixing Bacteria
VII. Effects of Pesticides on the Rhizosphere Microflora
VIII. Effects of Pesticides on Aquatic Microorganisms and
Phytoplankton
A. Direct Effects .
B. Indirect Effects
IX. Pesticide Interactions and Their Effects on Microorganisms
X. Miscellaneous Effects of Pesticides on Microorganisms .
A. Mutagenic Effects

B. Effects of Surfactants
LITERATURE CITED

13

IX

315
31 7
321
321
321
321
322
323
324
324
324
325
326
327
328
329
331
332
334
334
336
336
336
337

Effects of Pesticides on Nontarget Invertebrates in Freshwater

and Soil
A. R. THOMPSON and C. A. EDWARDS
I. Introduction.
A. Use of Pesticides in the USA
B. Movement of Pesticides Towards Waterways .
C. Types of Invertebrates in Soil and Freshwater
1. Eroding Bottoms .
2. Depositing Substrata
D. Scope of the Review .
II. Effects of Pesticides on Populations of Invertebrates in
Freshwater
A. Availability of Residues
B. Effects of Pesticides on Numbers of Plankton and Benthotic
Invertebrates
C. Repopulation of Contaminated Waters .
D. Ecological Effects of Freshwater Ecosystems.

341
341
341
343
344
344
345
345
345
347
354
356

Contents

III. Uptake of Sublethal Residues by Freshwater Invertebrates

IV. Effects of Pesticides on Populations of Invertebrates in Soil .
A. Nematodes
B. Mites
C. Springtails
D. Myriapods
1. Pauropods .
2. Symphylids .
3. Millipedes
4. Centipedes .
E. Earthworms
F . Molluscs .
G. Insects
V. Uptake of Pesticides into Soil Invertebrates
VI. A Comparison of the Effects of Pesticides on Freshwater and
Soil Invertebrates .
A. Persistence and Localization of Effects of Pesticides
B. Diversity of Species .
C. Biological Magnification of Pesticide Residues
D. Development of Resistance to Pesticides
E. Effects on the Behavior of Invertebrates
F. The Use of Indicator Species of Measure Contamination
G. Ecological Hazards of Pesticides .
LITERATURE CITED

14

357
360
360
361
362
363
363
363
364
364
364
365
365
366
368
369
370
371
371
372
373
374
375

Prevention and Detoxification of Pesticide Residues in Soils

ORVIN C. BURNSIDE
I. Avoiding Pesticide Residues in Soils .

General Situation
Integrated Pest Control
Use Minimum Dosage of Pesticides
Proper Application of Pesticides .
1. Formulation
2. Rate Used
3. Distribution.
4. Avoid Pesticide Movement From Target Area
E. Selected Short-Residual Pesticides
F. Pesticide Rotation
II. What to do Once You Have Pesticide Residues in Soil .
A. Summary of the Different Means of Dissipating Pesticide
Residues in Soils
1. Altering the Availability of Pesticides
2. Detoxifying the Pesticide
B. Practical Steps to Avoid Damage from Pesticide Residues
in Soils
1. Planting Tolerant Crops.
2. Using Plant Protectants .
3. Fallowing and Tilling the Land
4. Plowing to Incorporate the Pesticide
5. Irrigation
6. Adsorbents .
7. Microbial Additions
8. Chemical Addi tions
9. Future Solutions .
A.
B.
C.
D.

LITERATURE CITED

387
387
389
389
390
390
391
391
392
393
394
394
394
395
397
399
400
402
403
404
404
405
407
407
408
409

Contents
15

Xl

Removal of Organic Pesticides from Water to Improve Quality

HASSAN M. GOMAA and SAMUEL D. FAUST
I. Introduction.
II. Effect on Water Quality .
A. Taste and Odors
B. Toxicity to Fish
1. Pesticide Group A .
2. Pesticide Group B .
3. Other Pesticides
C. Water Quality Criteria
III. Treatment Processes for Potable Water
A. Chemical Oxidation .
B. Adsorption
1. Activated Carbon and Chemical Coagulation
2. Clay Minerals
C. Photodecomposition.
D. Ion Exchange .
E. Miscellaneous Processes
F. Operational and Efficiency Data .
IV. Treatment Processes for Waste Waters
V. Discussion
LITERATURE CITED

16

413
414
414
416
417
417
418
418
419
420
429
429
435
436
440
441
442
444
446
448

Extraction and Analytical Techniques for Pesticides in Soil,

Sediment, and Water
G. CHESTERS, H. B. PIONKE, and T. C. DANIEL
I. Sampling and Sample Preservation
A. Factors to be Considered Prior to Sample Collection
B. Soil Sampling .
C. Sampling Waters and Sediments .
D. Sample Preservation .
II. Extraction and Analysis of Pesticides in Soil, Sediment and
Water .
..
A. Extraction Procedures in Soil and Sediment Samples
1. Extraction of Organochlorine Insecticides from Soil
2. Extraction of Organochlorine Insecticides from
Suspended and Bottom Sediments
3. Extraction of Organophosphorus Pesticides from Soil
and Sediment
4. Extraction of Acidic Herbicides from Soil and Sedimen t
5. Extraction of Triazine Herbicides from Soil and Sediment
6. Extraction of Carbamate, Substituted Urea, Uracil, Anilide,
Aniline, Benzonitrile and Amide Pesticides from Soil
and Sediment
7. Extraction of Dipyridinium and Miscellaneous Pesticides
from Soil and Sediment.
B. Cleanup Procedures for Soil and Sediment Extracts.
1. Cleanup of Soil and Sedimen t Extracts for Determination
of Organochlorine Insecticides.
2. Cleanup of Soil and Sediment Extracts for Determination
of Organophosphorus Pesticides
3. Cleanup of Soil and Sediment Extracts for Determination
of Acidic Pesticides
4. Cleanup of Soil and Sedimen t Extracts for Determination
of Triazine Pesticides

451
452
453
453
455
456
457

459
464
465
466
467

467
470
470
501
503
504
505

Contents

XlI

5. Cleanup of Soil and Sediment Extracts for Determination

of Carbamate, Substituted Urea, Uracil, Anilide, Aniline,
Benzonitrile, and Amide Pesticides .
6. Cleanup of Soil and Sediment Extracts for Determination
of Dipyridinum and Miscellaneous Pesticides
C. Extraction and Cleanup of Waters
1. Extraction and Cleanup of Waters for Organochlorine
Insecticides .
2. Extraction and Cleanup of Waters for Organophosphorus
Pesticides
3. Extraction and Cleanup of Waters for Acidic Pesticides
4. Extraction and Cleanup of Waters for Carbama te,
Substituted Urea, Uracil, Benzonitrile, and
Amide Pesticides .
5. Extraction and Cleanup of Waters for Triazine,
Dipyridinium, and Other Pesticides .
D. Analysis of "Clean" Extracts
III. Systemized Monitoring of Soil, Sediment and Water
IV. Appendix
LITERATURE CITED
SUBJECT INDEX

506
508
508
509
516
517

524
525
532
533
534
539
551

FOREWORD
Soil scientists must understand and be able to manipulate the physical,
chemical, and biological properties of soils for the benefit of man. As the
world's population increases, the necessity for maintaining the productive
capacity of the soil also increases. Loss of productive capacity of the soil
through misuse, abuse, or neglect cannot occur without detrimental effects
on our food and natural-fiber supplies and will eventually bring harm to life
on the earth.
Production of adequate supplies of food and fiber requires that pesticides be used to reach and maintain a balance between the desired species
and competitors. Since pesticide usage is necessary and will likely increase,
soil scientists must stay in the forefront of knowledge about interactions between pesticides and soil and water. The almost infinite variation in physical,
chemical, and biological properties of soils and the variety of environments
in which they occur and in which pesticides are used necessitates numerous
and ex tensive research efforts.
The symposium sponsored by the Soil Science Society of America in
1965 resulted in the publication Pesticides and Their Effects on Soils and
Water. Demand required two additional printings of this volume. Since
pesticides are changing rapidly and knowledge about their use and behavior
is increasing, it became apparent that a more comprehensive treatment of
the subject, encompassing research results since 1965, was needed. This
volume Pesticides in Soil and Water will serve as an authoritative compendium of information for scientists, students, and laymen who desire information on this topic.
It is the hope of the Soil Science Society of America that this book will
accomplish the intended purpose of aiding in man's effort to provide food
and natural fiber without destroying the quality of the environment in which
he lives.
The Society is indebted to the organizing committee, the authors, the
editors, and the headquarters staff for their diligent and dedicated efforts
which made this publication possible.
Lubbock, Texas
May 1974
ANSON R. BERTRAND, president
Soil Science Society of America

Xlll

PREFACE
Pesticides in Soil and Water provides a comprehensive review of the principles
which control the environmental effects of pesticide-soil-water interactions.
The Soil Science Society of America published a book, Pesticides and Their
Effects on Soils and Water, as ASA Special Publication No.8 in 1966. Because of the large volume of research reports relating to pesticides which
have accumulated since that time, the executive committee of the Society
proposed an extensive revision of the book in 1971. The objective was to
provide an authoritative, in-depth, and up-to-date review of pesticides in
soils and water.
The book covers many facets of pesticide science including movement
in soil and surface water, adsorption, volatilization, degradation and persistence, plant uptake, curtailment and detoxification of pesticide residues in
soils, and sampling and analytic techniques for determination of pesticides in
soil, sediment, and water. In addition, the influence of pesticides on microorganisms in soil and water and on nontarget invertebrates in fresh water and
soil, are reviewed and discussed.
The editorial committee is sincerely appreciative of the cooperation it
has received from authors and reviewers, and for the continued advice on
manuscript processing provided by Matthias Stelly and Richard C. Dinauer
of the headquarters office.. The committee also acknowledges with gratitude
the contributions of T. J . Sheets of North Carolina State University who
served as chairman of this committee during portions of 1971 and 1972, and
had a major influence on the development of the basic format of the book.

May 1974
The Editorial Committee
W. D. GUENZI, chairman
USDA-ARS, Western Region
Fort Collins, Colorado

M. E. BLOODWORTH
Texas A & M University
College Station, Texas

J. L. AHLRICHS

G. CHESTERS
University of Wisconsin
Madison, Wisconsin

Purdue University
West Lafayette, Indiana

R.G.NASH
USDA-ARS, Northeast Region
Beltsville, Maryland
xv

CONTRIBUTORS
David E. Armstrong

Associate Professor, Water Chemistry Program, University

of Wisconsin, Madison, Wisconsin

William E. Beard

Chemist, Agricultural Research Service, U. S. Department

Agricul ture, Western Region, Fort Collins, Colorado

Rodney W. Bovey

Agronomist-Research Leader, Agricultural Research Service, U. S. Department of Agriculture, Department of Range

Science, Texas A&M University, College Station, Texas

Orvin C. Burnside

Professor of Weed Science, Department of Agronomy,

University of Nebraska, Lincoln, Nebraska

G. Chesters

Director of Water Resources Center, Professor of Soil Science, and Chairman of Water Chemistry Program, University
of Wisconsin, Madison, Wisconsin

T. C. Daniel

Assistan t Professor of Soil Science, Department of Soil

Science, University of Wisconsin, Madison, Wisconsin

Clive A. Edwards

Principal Scientific Officer, Rothamsted Experimental Station, Harpenden, Herts, England

Walter J. Farmer

Associate Professor of Soil Science and Associate Chemist,

Department of Soil Science and Agricultural Engineering,
University of California, Riverside, California

Samuel D. Faust

Professor, Department of Environmental Sciences, Rutgers,

The State University, New Brunswick, New Jersey

Hassan M. Gomaa

Manager, Research and Development Division, Keramchemie

Canada Limited, Don Mills, Ontario, Canada

Richard E. Green

Professor of Soil Science, Department of Agronomy and

Soil Science, University of Hawaii, Honolulu, Hawaii

Wayne D. Guenzi

Research Soil Scientist, Agricultural Research Service, U. S.

Department of Agriculture, Western Region, Fort Collins,
Colorado

Arthur E. Hiltbold

Professor of Soils, Agronomy and Soils Department, Auburn

University, Auburn, Alabama

Donald D. Kaufman

Research Soil Microbiologist, Pesticide Degradation Laboratory, Agricultural Environmental Quality Institute, Agricultural Research Service, U. S. Department of Agriculture,
Bel tsville, Mary land

John G. Konrad

Supervisor of Special Studies, Wisconsin Department of

Natural Resources, Madison, Wisconsin
XVll

XVIll

Contributors

John Letey

Professor of Soil Physics, Department of Soil Science and

Agricultural Engineering, University of California, Riverside,
California

Morris G. Merkle

Professor, Department of Soil and Crop Science, Texas

A&M University, College Station, Texas

Ralph G. Nash

Soil Scientist, Pesticide Degradation Laboratory, Agricultural Environmental Quality Institute, Agricultural Research
Service, U. S. Department of Agriculture, Beltsville, Maryland

James F. Parr

Microbiologist, Agricultural Research Service, U. S. Department of Agriculture, Southern Region, Baton Rouge,
Louisiana

Harry B. Pionke

Soil Scientist, Agricultural Research Service, U. S. Department of Agriculture, Southern Region, Chickasha, Oklahoma

Alwyn R. Thompson

Senior Scientific Officer, National Vegetable Research

Station, Wellesbourne, Warwick, England

Jerome B. Weber

Professor of Crop Science (Weed Science) and Soil Science,

Weed Science Center, North Carolina State University,
Raleigh, North Carolina

Sterling B. Weed

Professor, Department of Soil Science, North Carolina State

University, Raleigh, North Carolina

Conversion Factors for English and Metric Units

and Plant Nutrients
To convert
column 1
into column 2,
multiply by

Column 1

0.621
1. 094
0.394

kilometer, km
meter, m
centimeter, cm

O. 386
247.1
2.471

kilomete r2, km2

kilometer2, km2
hectare, ha

Column 2
LENGTH
mile, mi
yard, yd
inch, in

To convert
column 2
into column 1,
multiply by

1. 609
0.914
2.54

AREA

0.00973
3.532
2.838
0.0284
1. 057

meter3, mS
hectoliter, hI
hectoliter, hI
liter
liter

1. 102

2. 205

ton (metric)
quintal, q

2. 205
0.035

kilogram, kg
gram, g

mile 2 , mi 2
acre, acre
acre, acre
VOLUME
acre-inch
cubic foot, fts
bushel, bu
bushel, bu
quart (liquid), qt

2.590
0.00405
0.405

102. 8
0.2832
0.352
35.24
O. 946

MASS

14. 50
O. 9869
0.9678
14.22
14. 70

O. 446
O. 891
O. 891
1. 15

(f oc) +32

ton (English)
hundredweight,
cwt (short)
pound, lb
ounce (avdp), oz

PRESSURE
bar
Ib/inch2 , psi
bar
atmosphere,* atm
kg (weight)/ cm2
atmosphere,* atm
kg (weight)/cm2
Ib/inch2 , psi
atmosphere,* atm
lb/ inch2 , psi
YIELD OR RATE
ton (English)/ acre
ton (metric )/hectare
lb/acre
kg/ha
hundredweight/ acre
quintal/hectare
hectoliterfha, hl/ha
bu/acre

Celsius
-17.8 C
OC
20C
100C

TEMPERATURE
Fahrenheit

OF
32 F
68F
212 F

0.9072
0.454
O. 454
28.35

0.06895
1. 013
1. 033
0.07031
0.06805

2. 240
1. 12
1. 12

O. 87

2..(OF -32)

PLANT NUTRITION CONVERSION--P AND K

P (phosphorus) x 2. 29 = P 20 S
K (potassium) x 1. 20 = ~O
* The size of an "atmosphere" may be specified in either metric or English units.
XIX