bio degradation of surf

8/11/2019 bio degradation of surf

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S U R F C T N T B IO D E G R D T I O N

By

R. D. SWISHERMONSANTO COMPANYINOBGANIC CHEMICALS DIVISIONBESEABCH DEPABTMENT T LOUIS MISSOtJBI

1970

MARCEL DEKKER, INC., NEW YORK


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Preface v

List of Abbreviations xxi

1. BACKGROUND AND PERSPECTIVE 1

I. Detergent RevolutionEnvironmental Reaction 1

A. The Development of ABS 1B. The Wastewater Problem and Surfactant Biodegrada-

tion 1C. The Wastewater ProblemFocal Points 2

Cl. Sewage Treatment Processes 2C2. Surfactants in Sewage Treatment 3C3. Surfactants in Rivers 4C4. The Illinois River 4C5. The Neosho River 5C6. Groundwater 6

II . Biodegradation for Waste Surfactant Control 6

A. Definitions of Biodegradation 7B. Mixed Bacterial Systems 8C. Mixed Poods 9D. Temperature 9E. Oxygen 10F. Treatability and RemovalBiodegradation and Ad-

sorption 10G. Surfactant Removal by Chemical Means 11

III. Biodegradation Test Methods and Their Limitations 12

A. Typical Systems and Uncertainties 12

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I I . Surfactancy Methods 42

A. Foam 42A l. Applicability and Restrictions 42A2. Determination of Foaming Potential 43A3. Preconcentration by Foam Stripping 44

B . Surface Tension 45B l . Origin and Limitations 45B 2. Procedures 47

I I I . Specific Chemical Methods 47

A. Methylene Blue 47A l. Chemical Principle 47A2. Interferences 48A3. Procedures 49A4. Molecular Weight, Stoichiometry, and Calibration 50A5. MBASMethylene Blue Active Substances 51A6. Micromols, Milligrams, and Standards 51A7. Precision and Accuracy 52A8. Two-Phase Titration 53

B . Sulfate 54C. Polyethoxylate Nonionic Problems 54D. Cobalt Thiocyanate 55

D l . Principles and Procedures 55D 2. Intermediate Biodegradation Products 56

E. Bismuth Iodide-Barium Complexes; Mercuric Iodide 57F . Phosphotungstate, Phosphomolybdate 58

IV. Physicochemical Methods 59

A. Thin Layer Chromatography TLC) 59A l. General Principles \ 59A2. TLC Procedures 59

B . Gas Chromatography GC) 61B l . ABSDesulfonation-Gas Chromatography 61B 2. Aliphatic Sulfates and Sulfonates 62

B 3. Nonionics 62C. Infrared Spectroscopy 62

C l. General Ap plications 62C2. ABS in W ate rs and W aste waters 63C3. Differentiation of TBS and LAS 63


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D. Ultraviolet SpectroscopyBenzene Rings 63

E. Tracer Techniques 64V. Metabolic and Other Nonspecific Methods 65

A. Organic Content 66Al. Interferences and Uncertainties 66A2. Chemical Oxygen Demand COD) 67A3. Combustion 68A4. Gravimetric Determinations 69

B. OxygenBiochemical Oxygen Demand BOD) 69

Bl. Difficulties of Interpretation 69B2. Closed Bottle Techniques 70B 3. Respirometry 71

C. Carbon Dioxide 72D. Bacterial Growth 73E. Toxicity 74

4. THE BIOLOGICAL BACKGROUND 77

I. The Microorganisms 77A. Nonbacteria 77B. Bacterial Habitats and Species Distribution 78

II . Bacterial Development, Decline, and End Products; or,How Ultimate Is Ultimate Biodegradation? 80

A. An Idealized Picture 80

Al. Starvation to Plenty to Starvation 80A2. And Beyond Starvation 81

B. The Experimental Observations 82

III. Acclimation and Deacclimation 84

A. Induction of Enzymes 85B. Repression of Enzymes 87C. Degree of AcclimationBiodegradation Rates 89D. Thermal Acclimation and Temperature Effects 93

IV. Surfactant-Bacteria Interactions 96

A. Surfactants as Bacteriostats and Germicides 96Al . Conditions and Threshold Concentrations 96A2. Focal Points 100


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B . Continuous-Flow SystemsEquipment and Conditions 163C. The Official German Test Method 166D. Miniature Continuous-Flow Units 168E. Batch and Semicontinuous Systems 170

El . Batch Sludge Die-Away 170E2. The Romanian ISCH Test 171E 3. From Batch to Semicontinuous 171E4. The SDA Procedure 171E 5. Other Semicontinuous Procedures 172E6. Relation to Continuous Flow Systems 173

E7. Semicontinuous Arithmetic 174F. Steady and Unsteady) States 177

Fl . Bacterial PopulationsTheir Rise and Fall 177F2. Stabilizing Influences 177F 3 . Population Successions and Drifts 178F4. Acclimation 181F5. Mathematical Models 182F6. Bacterial Inhibition by Surfactants 184F7. Adsorption Effects 185

VIII. The SoilDrainage Fields and Lysimeters 186

IX. Anaerobic Systems 188A. Anaerobic Metabolism 188B . Die-Away Procedures 188C. Semicontinuous Operation 189D. Natural or Synthetic Feed? 189

X. Megatests and Field Tests 192

A. Advantages and Uncertainties; Analytical Interferences 192B . The Substitution Techniquethe Luton Test 193C. The Spiking Technique 194D. Field Tests Further Afield 195E. From Field to Real Life 197

XI. Biodegradation PotentialComparison of Methods 197

XII. Nonbiological Methods 201


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xiv ONTENTS

6. CHEMICAL STRUCTURE AND PRIMARY

BIODEGRADATION 203

I. Molecular Struc ture, Chain Branching, and Chain Length 203

I I . Alkylbenzenesulfonates 207A. Phenyl Position 207B . Chain Length 213

B l. LAS: InhibitionAcclimationDegradation 213B2. Limiting Concentrations for LAS Self-Inhibition 218B3. Linear Primary ABS 220

C. Chain BranchingMethyl Groups 220D. Quaternary Branching 223E. Cyclic Groups 225F. Multiple BranchingTB S 227

I I I . Other Alkylaryl Sulfonates 230

IV. Sulfonates from Aliphatic Hydrocarbons 233A. Alkane Sulfonates 233

B. Alkene and Hydroxyalkane Sulfonates 234

V. Sulfosuccinic Acid Esters 235

VI. Fa tty Acylamide Sulfonates 236

VII. Alkyl Sulfates 236

A. Branching 237B . Chain Length 238

VIII. Ethoxylate Sulfates 238

IX . Ethoxyla te Nonionics 243,A. Degree of Ethoxylation 243B. Alcohol Ethoxylates 243

B l. Hydrophobe Linearity 243B2. Alkyl Chain Length 247B3. Secondary Alcohols 247

C. Alkylphenol Ethoxylates 248Cl. Linear Alkyl Group 249C2. Branched Alkylphenols 251


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D. Other Ethoxylates 254

X. Miscellaneous Surfactants and Soaps 254

A. Soaps 255

7. METABOLIC PATHWAYS AND ULTIMATEBIODEGRADATION 257

I. Biochemical Oxidation 257

A. co-OxidationAliphatic Hydrocarbons 258B . /9-Oxidation 261C. Aromatic Oxidation 263D. Unsulfonated Alkylbenzenes 265

II. Biodegradation of Lower Sulfonates 268

A. Aromatic Sulfonates 269B . Aliphatic Sulfonates 272

III. The Biodegradation Process in LAS 274

A. Oxygen Uptake and Oxidation Products 275B . Initiation of Oxidation 277C. Alkyl Chain Oxidation 278D. Ring Degradation and Beyond 287

Dl. Detection of Benzene Rings by UV Analysis 288D2. Acclimation, Cross-Acclimation, and Pathways 289

IV. Quaternary Alkylbenzenesulfonates QBS) 294

A. Degradation of QBS 294

B . Mechanisms for Quaternary Biodegradation 296

V. Ultimate Biodegradation of TBS 299

VI. Sulfonated Esters and Amides 301

VII. Alkyl Sulfates and Ethoxylate Sulfates 302

A. Initial Hydrolysis or Initial Oxidation? 302B . Linear Primary Alkyl Sulfates 303


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xvi ONTENTS

Bl. Hydrolysis by Sulfatases 303B2. Oxidation of the Alcohol 304

B 3. Oxidation Before Hydrolysis 306B4. Anaerobic Oxidation 307

C. Secondary and Branched Alkyl Sulfates 308D. Ethoxylate Sulfates 310

VIII. Ethoxylate Nonionics 310

A. Unsubstituted Glycols and Polyglycols 311Al . Oxygen Uptake 311

A2. Oxidative Pathways 312B . Alcohol Ethoxylates 314Bl . Formation of Polyglycol or Polyglycol Carboxylate 314B2. Secondary and Branched Alcohol Ethoxylates 316

C. Alkylphenol Ethoxylates 317Cl. Oxygen Uptake 317C2. Weight Loss 317C3. UV Spectroscopy 319C4. The Course of Biodegradation 320

C5. Polypropylene APEs 321C6. Tertiary Octylphenol Ethoxylates 324C7. Linear Alkylphenol Ethoxylates 324

D. Ethoxylated Sugar Derivatives 325

8. BIODEGRADATION DATA 327

I. Organization and Scope of Tables 327

II . SubstrateChemical Nature: Column 1 327

III. Extent of Biodegradation: Column 2 330

IV. ConditionsTest Methods: Column 3 331

V. Biodegradation Time: Column 4 332

VI. Analytical Methods: Column 5 332

VII. Biodegradation Tables 334


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A. Anionic Su rfacta nts (Tables 8.1-8.15) 334A l . Ind ivid ual Alkylbenzenesulfonates 334

a. 6-Carbon Alk yl Gro up 334b. 8-Carbon Alk yl Grou p 334c. 9-Carbon Alkyl Grou p 334d. 10-Carbon Alkyl Grou p 334e. 11-Carbon Alky l G roup 335f. 12-Carbon Alky l G roup 335g. 13-Carbon Alky l G roup 337h, 14-Carbon Alky l Grou p 338i. 15-Carbon Alky l G roup 338 16-Carbon Alkyl Gro up 338k. 18-Carbon Alkyl Grou p 3381. Unsp ecified Size Alky l Grou p 338

A2. Linea r Alkylbenzenesu lfonates 340a. Indiv idua l Chain Len gths 340b. Mixed Chain Le ng ths 342

A3. TB S and Other Polypropylene Derivatives 350a. B elow C12 Alkyl Gro up 350b. Near C12 Alkyl Grou p 350c. Above C12 Alkyl Group 355d. Re lated Polypropylene Prod ucts 356

A4. Oth er Ty pes of AB S 357a. K B S (ex Kerosene) 357b. ex N onlin ear Olefins 357c. Oth er Cha racterized AB S 358d. Undisclosed or Unk now n Stru cture 358

A5. O ther Alky l Aro m atic Sulfonates 360a. ex Linear Di- an d Polyalkylben zenes 360b. ex Linear Alkyl B iphenyls 360c. ex Alkyl Na phth alenes 360d. ex Phe nylen e Alkanes 360e. Linear Thiaalkylbenzen esulfonates 360f. ex Alk ylph enols 361g. ex Alky lthiophen es 361

h. ex Carboxy alkylbenzenes 361A 6. Aliphatic Hydrocarbon and Hydroxyalkane Sul-fonates 362a. Line ar Pri m ary Alk ane Sulfonates 362b. Mixed Secondary Alkan e Sulfonates 362


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xviii ONTENTS

c. Alkene Sulfonates 363d. Hydroxyalkane Sulfonates 363

A7. Other Sulfonated Products 364a. a-Sulfo Fatty Acids and Derivatives 364b. Fa tty Acyl Isethionates 365c. Fatty Acyl Methyl Taurides 365d. Sulfosuccinic Acid Diesters 365e. Miscellaneous 366f. Unspecified or Unknown Structure 366

A8. Linear Primary Alkyl Sulfates 367

a. Alkyl Group Below C 12 367b. C 12 Alkyl Group 367c. Alkyl Group Above C 12 368d. Mixed Alkyl Groups 369e. Unspecified or Unknown Chain Length 370

A9. Other Primary Alkyl Sulfates 371a. Oxo Alcohols ex Linear Olefins 371b. Oxo Alcohols ex Polypropylenes, etc. 371c. Branched, Cyclic, Unsaturated, or Substituted

Alcohols 371d. Unspecified or Unknown Structure 372

A10. Secondary and Unknown Alkyl Sulfates 373a. Linear SecondaryIndividual Isomers 373b. Linear SecondaryMixed 373c. Nonlinear Secondary 373d. Unspecified or Unknown Structure 373

All . Alcohol Ethoxylate Sulfates 375

a. Linear Primary Alcohols 375b. Oxo Primary Alcohols ex Linear Olefins 375c. Oxo Primary Alcohols ex Tetrapropylene 375d. Other Primary Alcohols 375e. Linear Secondary Alcohols 375f. Other, Unspecified or Unknown Alcohols 376

A12. Alkylphenol Ethoxylate Sulfates 377a. Linear Primary Alkylphenols 377b. Linear Secondary Alkylphenols 377c. Linear + Branched Alkylphenols 377d. Branched or Unspecified Alkylphenols 377

A13. Other Sulfated Products 378A14. Phosphates, Phosphonates, Carboxylates, Soaps 379A15. MBAS in Sewage 380


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B . Nonionic Surfactants Tables 8.16-8.22) 381Bl. Linear Primary Alcohol Ethoxylates 381

a. Individual Chain Lengths 381b. Mixed or Unknown Chain Lengths 382

B2. Other Alcohol Ethoxylates 385a. Oxo Primary Alcohols ex Linear Olefins 385b. Oxo Primary Alcohols ex Tetrapropylene 385c. Linear Secondary Alcohol Ethoxylates 385d. Unspecified or Unknown Structure 386

B 3. Linear Alkylphenol Ethoxylates 387

a. Linear Primary Alkylphenols 387b. Linear Secondary Alkylphenols 387

B4. Branched or Unspecified Alkylphenol Ethoxylates 389a. Octyl Phenols 389b. Nonyl Phenols 390c. Dodecyl Phenols 391d. Di- and Polyalkyl Phenols 391e. Unknown or Unstated Alkyl Group 392

B5. Other Alkoxylate Derivatives 393a. Ethoxylates of Fa tty Acids and Fats 393b. Ethoxylates of Fatty Amides and Ethanol-

amides 393c. Ethoxylated Fatty Amines 394d. Ethoxylated Fatty Acyl Sorbitans 394e. Ethoxylated Sugar Derivatives 394f. Naphthalene Derivatives 394g. Ethylene-Propylene Oxide Derivatives 394h. Polyalkylene Oxides 394i. Ethoxylate Chlorides 394 Unspecified Structures 395k. CTAS in Sewage 395

B6. Sugar Derivatives 396a. Fatty Acyl Sucrose Derivatives 396b. Alkyl Sucrose Derivatives 396c. Sucroglyceride Ethoxylates 396

B7. Other Nonionics 397a. Fatty Alkanolamides 397b. Alkanesulfonyl Polypeptides 397c. Amine Oxides 397

C. Cationic Surfactants Table 8.23) 398D. Nonsurfactants Tables 8.24-8.29) 399


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xx ONTENTS

D l. Hydrocarbons 399a. Aliphatic 399b. Alicyclic 399c. Arom atic 399

D2. Alcohols 402a. Aliphatic 402b. Aromatic 403

D3. Glycols, Polyglycols, and Glycol Derivatives 404D4. Lower Sulfonates 406D5. Miscellaneous Aliphatics 408

a. Lower Carboxylates 408b. Ethanolamines 408c. Fats and Fat ty Derivatives 408d. Glucose 408e. Carboxym ethyl Cellulose 408f. Chelants 409

D6. Miscellaneous Aromatics 410a. Phenol and Derivatives 410b. Aniline and Derivatives 410c. Carboxylates 410

Bibliography /Author Index 411

Subject Index 469

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