SUPPORTING INFORMATION
PARAFAC modeling of irradiation- and oxidation-induced changes in fluorescent
dissolved organic matter extracted from poultry litter
Kiranmayi P. Mangalgiri
1, Stephen A. Timko
2, Michael Gonsior
3, and Lee Blaney
1*1:
University of Maryland Baltimore County
Department of Chemical, Biochemical and Environmental Engineering
1000 Hilltop Circle, ECS 314
Baltimore, MD 21250 USA
2:
Kennedy/Jenks Consultants
1191 2
ndAvenue, Suite 630
Seattle, WA 98101
3:
University of Maryland Center for Environmental Science
Chesapeake Biological Laboratory
146 Williams Street, P.O. Box 38
Solomons, MD 20688
* Corresponding author:
Lee Blaney, PhD
University of Maryland Baltimore County
Department of Chemical, Biochemical and Environmental Engineering
1000 Hilltop Circle, ECS 314
Baltimore, MD 21250 USA
Tel: +1-410-455-8608
Fax: +1-410-455-1049
Email: [email protected]
Summary:
Number of pages: 17
Number of tables: 3
Number of figures: 6
Table of Contents
Text
Text S1. Exploratory analysis of global and local EEM-PARAFAC models
S4
Tables
Table S1. Excitation loadings (arbitrary units) of the four-component global model
S7
Table S2. Emission loadings (arbitrary units) of the four-component global model
S9
Table S3. Core consistency and explained variance of final validated models
S13
Figures
Figure S1. Excitation and emission loadings of 3 – 13 component global EEM-PARAFAC
models generated during preliminary analysis
S6
Figure S2. Sum of squared errors plotted as a function of (a) excitation and (b) emission
wavelength. Observed, modeled, and residual EEMs are shown for the final
four-component global model for (c) untreated PLE1, (d) untreated PLE2, (e) untreated
PLE3, (f) PLE3 irradiated at 253.7 nm for 6 hours, (g) PLE3 irradiated at 310 – 410
nm for 6 hours, (h) PLE3 irradiated at 253.7 nm for 15 minutes with 24 mg H
2O
2/ g
DOC, and (i) PLE3 treated with 5.8 mg O
3/ g DOC
S11
Figure S3. Comparison of F
maxfor all components from global and local models of PLE1,
PLE2, and PLE3
S14
Figure S5. Change in fluorescence response of PLE2 for various treatments
S16
Figure S6. Change in fluorescence response of PLE3 for various treatments
S17
Text S1. Exploratory analysis of global and local EEM-PARAFAC models
The dataset consisted of 291 PLE samples which included untreated (6%), ozonated (12%),
samples irradiated at 310 – 410 nm (12%), samples irradiated at 253.7 nm (22%), and samples
treated with UV-H
2O
2for multiple doses of H
2O
2(48%). The decision to use four components in
the EEM-PARAFAC model was based on the shape of spectral loadings, split validation tests,
residual analysis, core consistency, and explained variance. The spectral loadings of preliminary
global models with 3 – 13 components are shown in Figure S1. EEM-PARAFAC models with
six or more components were not considered due to unrealistic spectral loadings for the
components in these models. Furthermore, high linearity in plots comparing two components
(‘compcorr’ plots) in six- and seven-component models (particularly for C3 and C6) suggested
that these components did not behave independently. The three-component model had
significantly higher residuals compared to the four- and five-components models. Hence, global
four- and five-component models were further investigated.
While the four-component model showed residuals at low wavelengths, incrementing the number
of components to five did not improve the residuals in this region. The sum of squared errors for
the four- and five-component models are provided in Figure S2a-b. The two models had
comparable explained variance. However, two of the components in the five-component model
(C4 and C5) showed significant linearity in the ‘compcorr’ plots. The core consistency fell
significantly for the five-component model (61.8%) compared to the four-component model
(80.4%). The four-component model was validated by split-half analysis. The excitation and
emission of the final four-component global model loadings are provided in Table S1 and Table
S2, respectively. Figure S2c-i shows the observed, modeled, and residual EEMs for select
treated and untreated PLEs.
For the local EEM-PARAFAC models, the same exploratory analysis protocols were followed.
The results were similar to those of the global model. Thus, four-component models were
investigated for further analysis of each PLE dataset. Table S3 lists the core consistency and
explained variance for the local and global models. The Tuckers congruence coefficient, a
measure of similarity, was greater than 0.99 for the spectral loadings in the global and local
models (as shown in Figure 2b-e ); the comparison of the F
maxfrom the global and local models
was close to the 1:1 line (see Figure S3). Based on these findings, the global four-component
model was used for all further analysis.
Figure S1. Excitation and emission loadings of 3 – 13 component global EEM-PARAFAC
models generated during preliminary analysis.
Table S1. Excitation loadings (arbitrary units) of the four-component global model.
Fluorescence data were obtained from a
1000× dilution of stock-PLE solutions made from one gram of poultry litter added to 25 mL DI water.
Wavelength (nm) C1 C2 C3 C4
240 2.19E-01 2.38E-01 3.50E-01 1.95E-01 243 2.00E-01 2.27E-01 3.69E-01 1.76E-01 246 1.80E-01 2.18E-01 3.81E-01 1.72E-01 249 1.61E-01 2.08E-01 3.76E-01 1.73E-01 252 1.42E-01 1.99E-01 3.50E-01 1.78E-01 255 1.25E-01 1.90E-01 3.14E-01 1.88E-01 258 1.11E-01 1.82E-01 2.75E-01 2.01E-01 261 9.90E-02 1.73E-01 2.29E-01 2.18E-01 264 9.01E-02 1.65E-01 1.85E-01 2.36E-01 267 8.57E-02 1.58E-01 1.54E-01 2.56E-01 270 8.43E-02 1.53E-01 1.31E-01 2.75E-01 273 8.60E-02 1.47E-01 1.10E-01 2.88E-01 276 9.00E-02 1.40E-01 8.97E-02 2.91E-01 279 9.62E-02 1.32E-01 7.08E-02 2.84E-01 282 1.05E-01 1.25E-01 5.30E-02 2.67E-01 285 1.15E-01 1.18E-01 3.62E-02 2.42E-01 288 1.28E-01 1.12E-01 2.25E-02 2.14E-01 291 1.42E-01 1.07E-01 1.35E-02 1.81E-01 294 1.54E-01 1.03E-01 6.16E-03 1.49E-01 297 1.66E-01 9.96E-02 1.45E-03 1.21E-01 300 1.77E-01 9.61E-02 0.00E+00 9.85E-02 303 1.87E-01 9.27E-02 0.00E+00 7.95E-02 306 1.95E-01 8.99E-02 0.00E+00 6.34E-02 309 2.02E-01 8.75E-02 0.00E+00 5.03E-02 312 2.06E-01 8.60E-02 0.00E+00 3.98E-02 315 2.09E-01 8.54E-02 0.00E+00 3.05E-02 318 2.10E-01 8.55E-02 0.00E+00 2.21E-02 321 2.09E-01 8.70E-02 0.00E+00 1.46E-02
Wavelength (nm) C1 C2 C3 C4
324 2.07E-01 8.93E-02 0.00E+00 7.89E-03 327 2.03E-01 9.22E-02 0.00E+00 1.87E-03 330 1.95E-01 9.59E-02 0.00E+00 0.00E+00 333 1.86E-01 9.98E-02 0.00E+00 0.00E+00 336 1.75E-01 1.04E-01 0.00E+00 0.00E+00 339 1.62E-01 1.08E-01 0.00E+00 0.00E+00 342 1.49E-01 1.12E-01 0.00E+00 0.00E+00 345 1.36E-01 1.15E-01 0.00E+00 0.00E+00 348 1.23E-01 1.18E-01 0.00E+00 0.00E+00 351 1.10E-01 1.21E-01 0.00E+00 0.00E+00 354 9.82E-02 1.23E-01 0.00E+00 0.00E+00 357 8.66E-02 1.25E-01 0.00E+00 0.00E+00 360 7.55E-02 1.27E-01 0.00E+00 0.00E+00 363 6.55E-02 1.28E-01 0.00E+00 0.00E+00 366 5.60E-02 1.28E-01 0.00E+00 0.00E+00 369 4.70E-02 1.27E-01 0.00E+00 0.00E+00 372 3.88E-02 1.26E-01 0.00E+00 0.00E+00 375 3.14E-02 1.25E-01 0.00E+00 0.00E+00 378 2.47E-02 1.22E-01 0.00E+00 0.00E+00 381 1.88E-02 1.19E-01 0.00E+00 0.00E+00 384 1.40E-02 1.16E-01 0.00E+00 0.00E+00 387 9.50E-03 1.13E-01 0.00E+00 0.00E+00 390 5.50E-03 1.09E-01 0.00E+00 0.00E+00 393 1.86E-03 1.05E-01 0.00E+00 0.00E+00 396 0.00E+00 1.00E-01 0.00E+00 0.00E+00 399 0.00E+00 9.49E-02 0.00E+00 0.00E+00 402 0.00E+00 8.92E-02 0.00E+00 0.00E+00 405 0.00E+00 8.35E-02 5.74E-06 0.00E+00
Wavelength (nm) C1 C2 C3 C4 408 0.00E+00 7.79E-02 1.16E-05 0.00E+00 411 0.00E+00 7.24E-02 1.68E-05 0.00E+00 414 0.00E+00 6.71E-02 2.14E-05 0.00E+00 417 0.00E+00 6.22E-02 2.58E-05 0.00E+00 420 0.00E+00 5.75E-02 2.93E-05 0.00E+00 423 0.00E+00 5.32E-02 3.20E-05 0.00E+00 426 0.00E+00 4.90E-02 3.62E-05 0.00E+00 429 0.00E+00 4.50E-02 3.89E-05 0.00E+00 432 0.00E+00 4.10E-02 4.18E-05 0.00E+00 435 0.00E+00 3.72E-02 4.23E-05 0.00E+00 438 0.00E+00 3.36E-02 4.50E-05 0.00E+00 441 0.00E+00 3.03E-02 4.57E-05 0.00E+00 444 0.00E+00 2.71E-02 4.57E-05 0.00E+00 447 0.00E+00 2.42E-02 4.59E-05 0.00E+00 450 0.00E+00 2.18E-02 4.52E-05 0.00E+00 453 0.00E+00 1.98E-02 4.48E-05 0.00E+00 456 0.00E+00 1.79E-02 4.41E-05 0.00E+00 459 0.00E+00 1.62E-02 4.41E-05 0.00E+00 462 0.00E+00 1.46E-02 4.38E-05 0.00E+00 465 0.00E+00 1.32E-02 4.34E-05 0.00E+00 468 0.00E+00 1.19E-02 4.25E-05 0.00E+00 471 0.00E+00 1.07E-02 4.18E-05 0.00E+00 474 0.00E+00 9.56E-03 3.99E-05 0.00E+00 477 0.00E+00 8.37E-03 3.77E-05 0.00E+00 480 0.00E+00 7.27E-03 3.71E-05 0.00E+00 483 0.00E+00 6.54E-03 3.46E-05 0.00E+00 486 0.00E+00 5.79E-03 3.30E-05 0.00E+00 489 0.00E+00 5.08E-03 3.13E-05 0.00E+00 492 0.00E+00 4.43E-03 2.98E-05 0.00E+00 495 0.00E+00 3.89E-03 2.84E-05 0.00E+00
Wavelength (nm) C1 C2 C3 C4
498 0.00E+00 3.39E-03 2.67E-05 0.00E+00 501 0.00E+00 2.92E-03 2.54E-05 0.00E+00 504 0.00E+00 2.56E-03 2.41E-05 0.00E+00 507 0.00E+00 2.25E-03 2.22E-05 0.00E+00 510 0.00E+00 1.94E-03 2.14E-05 0.00E+00 513 0.00E+00 1.74E-03 2.03E-05 0.00E+00 516 0.00E+00 1.54E-03 1.88E-05 0.00E+00 519 0.00E+00 1.34E-03 1.69E-05 0.00E+00
Table S2. Emission loadings (arbitrary units) of the four-component global model.
Fluorescence data were obtained from a
1000× dilution of stock-PLE solutions made from one gram of poultry litter added to 25 mL DI water. Emission wavelengths have
been rounded to the nearest whole number.
Wavelength (nm) C1 C2 C3 C4
243 0.00E+00 0.00E+00 0.00E+00 0.00E+00 246 3.86E-05 0.00E+00 3.91E-04 7.77E-06 249 9.60E-05 0.00E+00 1.19E-03 2.85E-05 252 1.50E-04 0.00E+00 2.67E-03 1.08E-04 255 1.82E-04 0.00E+00 4.69E-03 2.92E-04 258 1.89E-04 0.00E+00 6.96E-03 5.80E-04 261 1.70E-04 0.00E+00 9.43E-03 1.00E-03 264 0.00E+00 1.71E-04 1.29E-02 1.70E-03 267 0.00E+00 3.39E-04 1.86E-02 2.75E-03 270 0.00E+00 6.02E-04 2.80E-02 4.54E-03 273 0.00E+00 7.77E-04 4.35E-02 7.33E-03 276 0.00E+00 7.24E-04 6.63E-02 1.14E-02 279 0.00E+00 8.99E-04 1.01E-01 1.76E-02 282 0.00E+00 3.72E-04 1.41E-01 2.51E-02 285 0.00E+00 0.00E+00 1.86E-01 3.43E-02 288 0.00E+00 0.00E+00 2.30E-01 4.59E-02 291 0.00E+00 0.00E+00 2.75E-01 5.91E-02 294 0.00E+00 0.00E+00 3.16E-01 7.36E-02 297 0.00E+00 0.00E+00 3.32E-01 9.13E-02 300 0.00E+00 0.00E+00 3.32E-01 1.10E-01 303 0.00E+00 0.00E+00 3.21E-01 1.24E-01 306 0.00E+00 0.00E+00 3.00E-01 1.42E-01 309 0.00E+00 0.00E+00 2.72E-01 1.61E-01 312 0.00E+00 0.00E+00 2.42E-01 1.78E-01 315 0.00E+00 0.00E+00 2.13E-01 1.93E-01 318 0.00E+00 0.00E+00 1.85E-01 2.05E-01 321 1.68E-03 0.00E+00 1.57E-01 2.13E-01
Wavelength (nm) C1 C2 C3 C4
324 4.95E-03 0.00E+00 1.31E-01 2.18E-01 327 8.80E-03 0.00E+00 1.08E-01 2.20E-01 330 1.29E-02 0.00E+00 8.79E-02 2.20E-01 333 1.79E-02 0.00E+00 7.05E-02 2.18E-01 336 2.38E-02 0.00E+00 5.59E-02 2.15E-01 339 3.12E-02 0.00E+00 4.36E-02 2.11E-01 342 4.01E-02 0.00E+00 3.35E-02 2.06E-01 345 4.98E-02 0.00E+00 2.54E-02 1.99E-01 348 6.05E-02 0.00E+00 1.82E-02 1.92E-01 351 7.23E-02 0.00E+00 1.24E-02 1.83E-01 354 8.52E-02 0.00E+00 7.14E-03 1.74E-01 357 9.88E-02 0.00E+00 3.76E-03 1.65E-01 360 1.13E-01 0.00E+00 4.42E-04 1.58E-01 363 1.28E-01 0.00E+00 0.00E+00 1.51E-01 366 1.43E-01 0.00E+00 0.00E+00 1.44E-01 369 1.58E-01 0.00E+00 0.00E+00 1.38E-01 372 1.74E-01 0.00E+00 0.00E+00 1.32E-01 375 1.88E-01 0.00E+00 0.00E+00 1.25E-01 378 2.01E-01 0.00E+00 0.00E+00 1.20E-01 381 2.13E-01 0.00E+00 0.00E+00 1.14E-01 384 2.20E-01 6.36E-03 0.00E+00 1.07E-01 387 2.23E-01 1.60E-02 0.00E+00 1.00E-01 390 2.25E-01 2.63E-02 0.00E+00 9.43E-02 393 2.26E-01 3.63E-02 0.00E+00 8.80E-02 396 2.25E-01 4.73E-02 0.00E+00 8.28E-02 399 2.21E-01 5.86E-02 0.00E+00 7.77E-02 402 2.17E-01 7.00E-02 0.00E+00 7.30E-02
Wavelength (nm) C1 C2 C3 C4 405 2.11E-01 8.16E-02 0.00E+00 6.87E-02 408 2.03E-01 9.34E-02 0.00E+00 6.46E-02 411 1.95E-01 1.04E-01 0.00E+00 6.06E-02 414 1.86E-01 1.15E-01 0.00E+00 5.74E-02 417 1.78E-01 1.25E-01 0.00E+00 5.43E-02 420 1.69E-01 1.35E-01 0.00E+00 5.14E-02 423 1.60E-01 1.45E-01 0.00E+00 4.88E-02 426 1.51E-01 1.53E-01 0.00E+00 4.64E-02 429 1.41E-01 1.60E-01 0.00E+00 4.40E-02 432 1.31E-01 1.66E-01 0.00E+00 4.19E-02 435 1.22E-01 1.71E-01 0.00E+00 3.98E-02 438 1.13E-01 1.75E-01 0.00E+00 3.85E-02 441 1.04E-01 1.78E-01 0.00E+00 3.68E-02 444 9.58E-02 1.82E-01 0.00E+00 3.49E-02 447 8.79E-02 1.83E-01 0.00E+00 3.31E-02 450 8.04E-02 1.84E-01 0.00E+00 3.19E-02 453 7.35E-02 1.84E-01 0.00E+00 3.01E-02 456 6.69E-02 1.84E-01 0.00E+00 2.87E-02 459 6.09E-02 1.82E-01 0.00E+00 2.76E-02 462 5.53E-02 1.81E-01 0.00E+00 2.64E-02 465 5.02E-02 1.79E-01 0.00E+00 2.53E-02 468 4.55E-02 1.77E-01 0.00E+00 2.43E-02 471 4.12E-02 1.74E-01 0.00E+00 2.34E-02 474 3.72E-02 1.72E-01 0.00E+00 2.26E-02 477 3.34E-02 1.68E-01 0.00E+00 2.21E-02 480 3.01E-02 1.65E-01 0.00E+00 2.14E-02 483 2.69E-02 1.60E-01 0.00E+00 2.11E-02 486 2.41E-02 1.56E-01 0.00E+00 2.09E-02 489 2.14E-02 1.52E-01 0.00E+00 2.09E-02 492 1.90E-02 1.47E-01 0.00E+00 2.07E-02
Wavelength (nm) C1 C2 C3 C4
495 1.70E-02 1.43E-01 0.00E+00 2.04E-02 498 1.51E-02 1.39E-01 0.00E+00 2.00E-02 501 1.34E-02 1.34E-01 0.00E+00 1.95E-02 504 1.19E-02 1.29E-01 0.00E+00 1.88E-02 507 1.05E-02 1.23E-01 0.00E+00 1.79E-02 510 9.36E-03 1.17E-01 0.00E+00 1.70E-02 513 8.27E-03 1.12E-01 0.00E+00 1.64E-02 516 7.29E-03 1.08E-01 0.00E+00 1.60E-02 519 6.46E-03 1.04E-01 0.00E+00 1.56E-02 522 5.83E-03 9.94E-02 0.00E+00 1.51E-02 525 5.29E-03 9.47E-02 0.00E+00 1.44E-02 528 4.59E-03 8.97E-02 0.00E+00 1.41E-02 531 4.03E-03 8.46E-02 1.06E-04 1.35E-02 534 3.51E-03 7.97E-02 5.18E-04 1.33E-02 537 3.06E-03 7.53E-02 7.63E-04 1.32E-02 540 2.61E-03 7.16E-02 9.52E-04 1.36E-02 543 2.23E-03 6.82E-02 1.19E-03 1.36E-02 546 2.11E-03 6.46E-02 1.50E-03 1.31E-02 549 1.83E-03 6.08E-02 2.41E-03 1.29E-02 552 1.71E-03 5.70E-02 3.19E-03 1.23E-02 555 1.58E-03 5.28E-02 4.30E-03 1.16E-02 558 1.62E-03 4.88E-02 5.19E-03 1.09E-02 561 1.49E-03 4.55E-02 5.79E-03 1.04E-02 564 1.34E-03 4.24E-02 6.10E-03 1.00E-02 567 1.42E-03 4.08E-02 4.43E-03 9.49E-03
