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8. Kujawinski, E. B.; Hatcher, P. G.; Freitas, M. A. 2002, Anal. Chem. 74, 413-419. 9. Brown, T. L.; Rice, J. A. 2000, Anal. Chem. 72, 384-390. 10. Hertkorn, N.; Benner, R.; Frommberger, M.; Schmitt-Kopplin, P.; Witt, M.; Kaiser, K.; Kettrup, A.; Hedges, J. I. 2006, Geochim. Et Cosmochim. Acta 70, 2990-3010. 11. Ritchie, J. D.; Perdue, E. M. 2003, Geochim. Et Cosmochim. Acta 67, 85-96. 12. Perdue, E. M. 1985, In Humic substances in soil sediment and water. Geochemistry, isolation and characterisation; Aiken, G. R., McKnight, D. M., Wershaw, R. L., MacCarthy, P., Eds.; Wiley-Interscience: New York, pp 493-526. 13. Stenson, A. C.; Landing, W. M.; Marshall, A. G.; Cooper, W. T. 2002, Anal. Chem. 74, 4397- 4409. 14. Kanu, A. B.; Dwivedi, P.; Tam, M.; Matz, L.; Hill Jr., H. H. 2008, J. of Mass Spectrom. 43, 1-22. 18
Depicting Molecular Dissimilarity in Complex Materials Norbert Hertkorn 1 , M. Frommberger 1 , Ph. Schmitt-Kopplin 1 , E. M. Perdue 2 1 Institute of Ecological Chemistry, Helmholtz Zentrum Muenchen, German Research Center for Environmental Health, Ingolstaedter Landstrasse 1, D-85764 Neuherberg, Germany, hertkorn@helmholtz-muenchen.de 2 School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, Georgia, 30332, USA Keywords: NOM, compositional space, intrinsic averaging, isomers, complexity 1. INTRODUCTION Natural complex organic materials if classified by their means of synthesis and function divide into discrete molecules which often derive from genetic codes that can be fractionated into unambiguously defined molecular fractions within the scope of current high-performance separation technology, and complex non-repetitive materials which cannot be purified in the conventional meaning of purity because of even higher intricacy. The fate of this vast group of molecules in the bio- and geosphere is governed according to the rather fundamental restraints of thermodynamics and kinetics. In these intricate materials, the “classical” signatures of the (often ultimately biotic) precursor molecules, like lipids, glycans, proteins have been attenuated, often beyond recognition, during a succession of biotic and abiotic (e.g. photo- and redox chemistry) reactions (1). Because of this loss of biochemical signature, these materials can be designated nonrepetitive complex systems. Examples include freshwater, marine, and soil organic matter, kerogens and aerosols, among others. 2. MATERIALS AND METHODS The findings mentioned here have been derived over several years from multinuclear high-field (11.7 T) NMR spectra and high-field (9.4 and 12 T) FTICR mass spectra of natural organic matter (NOM) samples of terrestrial, freshwater and marine origin. 3. RESULTS AND DISCUSSION The current perception of natural organic matter (NOM) molecular structure is defined by the available analytical methods, which typically depict data-reduced projections of the chemical structure space (i. e., the complement of all chemical structures present in NOM). Related to the true molecular diversity of NOM, the extent of data reduction encountered in any spectra or chromatograms always ranges in the extremes. Accordingly, severe intrinsic averaging, caused by a non-avoidable, massive signal overlap masks molecularlevel alterations of NOM in any standard analytical technique. For similar reasons, bulk properties of NOM, like elemental ratios and acidity, regularly fall within remarkably narrow ranges (Figure 1). 19
Page 1 and 2: Volume I From Molecular Understandi
Page 3 and 4: Dedication to the memory of Profess
Page 5 and 6: Organizing Committee Lunin, Valery,
Page 7 and 8: Preface The 20 th century was the c
Page 9 and 10: Dear colleagues and friends of humi
Page 11 and 12: On behalf of the International Unio
Page 13: On behalf of the Government of Mosc
Page 16 and 17: Insights into the Composition of Hu
Page 18 and 19: Section II - Natural organic matter
Page 20 and 21: Distribution of Water Soluble Organ
Page 22 and 23: Comparison of 13 C NMR Spectra of F
Page 24 and 25: Effect of Humic Substances on Metal
Page 26 and 27: Hybrid Sorbents on the Basis of Mag
Page 28 and 29: Structural Components and Biologica
Page 30 and 31: The Effect of Bioaugmentation on th
Page 33 and 34: Agent-Based Modeling of Natural Org
Page 35 and 36: 17 16 Cu(II) Binding Titration pCu
Page 37 and 38: Probing Local pH in Hydrophobic Dom
Page 39 and 40: In each experiment, the intensity o
Page 41 and 42: Study on Self-Assembling Mechanism
Page 43 and 44: 3. RESULTS AND DISCUSSION HRUS has
Page 45 and 46: Multiple Charged Constituents in Su
Page 47: supermixtures. Although we have to
Page 51 and 52: Molecular level precision analytica
Page 53 and 54: Isolation and Characterization of H
Page 55 and 56: -10 net proton surface excess, mmol
Page 57 and 58: Hydrous Pyrolysis of Natural Organi
Page 59 and 60: a) b) Time (min) 10 20 30 40 50 60
Page 61 and 62: High Resolution and Hyphenated Anal
Page 63 and 64: mixtures - molecular inventory need
Page 65 and 66: X-Ray Spectromicroscopy of Organic
Page 67 and 68: Figure 1. Transmission X-ray micros
Page 69 and 70: Effects of pH, Temperature, and Org
Page 71 and 72: Figure 1. a) Dissolution curves of
Page 73 and 74: Spectroscopic Evaluation of Charcoa
Page 75 and 76: Table 1. Ratios of the measured UV-
Page 77 and 78: Properties of Hydration Shell of IH
Page 79 and 80: from that ice which was attributed
Page 81 and 82: Insights into the Composition of Hu
Page 83 and 84: Figure 2. 13 C Bloch Decay NMR spec
Page 85 and 86: Characterization of Soil Organic Ma
Page 87 and 88: Table 2. The Alkyl-C/O-Alkyl-C rati
Page 89 and 90: Characterization of Chernozem Humic
Page 91 and 92: The DRIFT spectra of humic fraction
Page 93 and 94: Autodock Simulation of Interactions
Page 95 and 96: Structural Characteristics of Soil
Page 97 and 98: 3.3. Thermal properties of HMi and
Page 99 and 100:
A Water Soluble Polymer as a Workin
Page 101 and 102:
Leonardite HA Synthetic HA Absorban
Page 103 and 104:
Characterization of Humic Acids fro
Page 105 and 106:
Random Generation of 3D Structures
Page 107 and 108:
Biodegradation of Humic Acid by Whi
Page 109 and 110:
non-exchangeable protons shown in T
Page 111 and 112:
Limitations in High Resolution NMR
Page 113 and 114:
Investigation of Chemical Structure
Page 115 and 116:
1037, 1375; lower ones at m/z 537,
Page 117 and 118:
Spectral Characterization of Plant-
Page 119 and 120:
DOM sources were primarily composed
Page 121 and 122:
Capillary Electrophoresis and Fluor
Page 123 and 124:
2). Component 1 was most sensitive
Page 125 and 126:
Characterization of Synthetic (Core
Page 127 and 128:
Magnetic Field Laboratory in Tallah
Page 129 and 130:
High Resolution Ultrasonic Spectros
Page 131 and 132:
40 35 30 25 N (1/m) 20 15 10 5 0 -5
Page 133 and 134:
Characterization of Mumijo (Shilaji
Page 135 and 136:
Extraction and Characterisation of
Page 137 and 138:
possible aggregating compounds, suc
Page 139 and 140:
Measuring Soil Amino Compounds by A
Page 141 and 142:
individual amino compounds (Table 1
Page 143 and 144:
Membrane Processes Applied to the S
Page 145 and 146:
3. RESULTS AND DISCUSSION The resul
Page 147 and 148:
Studies of the Structure of Extract
Page 149 and 150:
Figure 3. The XRD pattern. Figure 4
Page 151 and 152:
Application of a Novel Polarity Met
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1.00 0.90 0.80 Retention Coefficien
Page 155 and 156:
Separation and Isolation of Soil Hu
Page 157 and 158:
uffer at a level 1%. Urea assists i
Page 159 and 160:
NMR Approaches for Characterization
Page 161 and 162:
structure and functionality among t
Page 163 and 164:
Comparison of Humic Acid and Metal
Page 165 and 166:
The negative area after the hump in
Page 167 and 168:
Comparison of Mumijo (Shilajit) and
Page 169 and 170:
Solid Phase Micro Extraction (SPME)
Page 171 and 172:
3. RESULTS AND DISCUSSION Our first
Page 173:
Section II Natural organic matter a
Page 176 and 177:
Many methods of soil chemistry (suc
Page 178 and 179:
5. ACKNOWLEDGMENTS RFBR grant № 0
Page 180 and 181:
etween 1893 and 1900 i.e. Kozlovski
Page 182 and 183:
2. MATERIALS AND METHODS Lake water
Page 184 and 185:
System a Depth Season Type of syste
Page 186 and 187:
egion, absorption at 1384 cm −1 ,
Page 188 and 189:
may lie in the ultrafiltration beha
Page 190 and 191:
during the first 3 days. As indicat
Page 192 and 193:
4. SUMMARY AND CONCLUSIONS Our stud
Page 194 and 195:
• Certain biomacromolecules are o
Page 196 and 197:
other fossil fuels). These hydrates
Page 198 and 199:
and 6607 ± 79 yr at 50-100 cm. Aci
Page 200 and 201:
Table 2. The dynamics of analytical
Page 202 and 203:
as minimally dependent on climatic
Page 204 and 205:
Table 1. The carbon species content
Page 206 and 207:
3. RESULTS AND DISCUSSION Paramagne
Page 208 and 209:
calibrated against KCl and Radiomet
Page 210 and 211:
4. CONCLUSIONS Increased frequency
Page 212 and 213:
and solid state 13 C-CPMAS-NMR usin
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of these groups revealed the domina
Page 216 and 217:
each plot soil was sampled from the
Page 218 and 219:
Microbial species for test were ind
Page 220 and 221:
4. CONCLUSIONS The results of FT-IR
Page 222 and 223:
degraders using the natural organic
Page 224 and 225:
4. CONCLUSIONS The results showed a
Page 226 and 227:
whole soil and the HF treated sampl
Page 228 and 229:
Table 1. Sample depth, C and N valu
Page 230 and 231:
3. RESULTS AND DISCUSSION Chemical
Page 232 and 233:
in TL spectrum of P-HA sample, whic
Page 234 and 235:
Humic and fulvic acids were separat
Page 236 and 237:
An important role in determining so
Page 238 and 239:
The number of plots found for each
Page 240 and 241:
Table 1. T50 for DTG. Data are mean
Page 242 and 243:
Histosols for both layers 0-25 and
Page 244 and 245:
Cambisols 27,6% Acrisols 0,1% Chern
Page 246 and 247:
2 ml) at room temperature for 16 ho
Page 248 and 249:
lipid composition occured. On the o
Page 250 and 251:
abandoned about 30 years ago; 4 pin
Page 252 and 253:
4. CONCLUSIONS C associated to the
Page 254 and 255:
m). In each soil sample pH (H 2 O a
Page 256 and 257:
main fraction in E and EB horizons,
Page 258 and 259:
0 5 depth in cm 10 15 20 average C3
Page 260 and 261:
REFERENCES 1. Steinbeiss, S., Beßl
Page 262 and 263:
Conductivity and pH was determined
Page 264 and 265:
REFERENCES 1. Aiken G.R. 1985. Isol
Page 266 and 267:
MAS) 13 C NMR spectra were obtained
Page 268 and 269:
REFERENCES 1. Shoji, S., Nanzyo, M.
Page 270 and 271:
Table 1. Distribution of size fract
Page 272 and 273:
Relative fluorescence intensity Hum
Page 274 and 275:
water extract) used in this study.
Page 276 and 277:
Table 1. Some related information a
Page 278 and 279:
iomass, they utilize remnants of th
Page 280 and 281:
mg l -1 CU 4 3 2 1 0 4 2 Colour DOC
Page 282 and 283:
ACKNOWLEDGEMENT We thank the resear
Page 284 and 285:
temperature (T) and conversion (α)
Page 286 and 287:
showed a sudden increase in kinetic
Page 288 and 289:
CL -1 in 0,02 M NaHCO 3. Degree of
Page 290 and 291:
indices of HA are greatly influence
Page 292 and 293:
solutions of alpha-radioactive elem
Page 294 and 295:
and RF Ministry of Education and Sc
Page 296 and 297:
analysis standard methods were used
Page 298 and 299:
environment can be improved only wi
Page 300 and 301:
Table 1. Characteristics of Lake V
Page 302 and 303:
DOC, mg/L a CDOM (254) A250/A360 F(
Page 304 and 305:
2. MATERIALS AND METHODS The resear
Page 306 and 307:
A soil system passes the irreversib
Page 308 and 309:
method, whereas sterols were purifi
Page 310 and 311:
3. RESULTS AND DISCUSSION For the m
Page 312 and 313:
3. RESULTS AND DISCUSSION In a gene
Page 314 and 315:
4. CONCLUSIONS All the FTIR, DRUV-V
Page 316 and 317:
3. RESULTS AND DISCUSSION Variabili
Page 318 and 319:
4. CONCLUSIONS 1. The diverse granu
Page 320 and 321:
ESI FT-ICR mass spectra were acquir
Page 322 and 323:
The first autumn storm, beginning 1
Page 324 and 325:
4. CONCLUSIONS DOC, DON, SUVA and T
Page 326 and 327:
Sample NaPT d = 1.6 Sonication Cent
Page 328 and 329:
A number of aromatic compounds have
Page 330 and 331:
The Gumat-80 preparation (“Gumat
Page 332 and 333:
BRHE Program; Grant of “Molecular
Page 334 and 335:
3. RESULTS AND DISCUSSION In this s
Page 336 and 337:
of the key parameters describing po
Page 338 and 339:
The formula of Determan (Determan,
Page 340 and 341:
that the process of humification wi
Page 342 and 343:
HF. The humic fractions were charac
Page 344 and 345:
unaltered plant debris, BC and alip
Page 346 and 347:
3. RESULTS AND DISCUSSIONS Decompos
Page 348 and 349:
Initial recoveries of new C within
Page 350 and 351:
25-30 % from the contents of the no
Page 352 and 353:
REFERENCES 1. Gorbunov, N. I. 1963.
Page 354 and 355:
3. RESULTS AND DISCUSSION Elemental
Page 356 and 357:
whereas the HAL from the P series e
Page 358 and 359:
Emission spectra were recorded over
Page 360 and 361:
The EEM spectra of HALs (Figure 2)
Page 362 and 363:
amounts of organic sulfur, up to 14
Page 364 and 365:
The FA samples were isolated and pu
Page 366 and 367:
Alkyl-C (1), (2) proportions in the
Page 368 and 369:
degree of aromaticity (6) and molec
Page 370 and 371:
REFERENCES 1. Kalbitz, K., Geyer, S
Page 372 and 373:
elative lignin content of fresh tis
Page 374 and 375:
4. CONCLUSIONS The debris of pine f
Page 376 and 377:
2. MATERIALS AND METHODS Soil surve
Page 378 and 379:
REFERENCES 1. Saparov A. S. 2007. S
Page 380:
The CO 2 evolved was trapped by 0.5
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