Figure 1.
Gas chromatography–mass spectrometry (GC-MS) presenting the storage stability of stilbene glycosides of Norway spruce (Picea abies [L] Karst) bark: fresh bark at sawmill (a); 1-year-stored bark at a sawmill (b); and size exclusion chromatography results of fresh (blue line, unimodal) and 1-year stored bark (red line, bimodal) (c).
Figure 1.
Gas chromatography–mass spectrometry (GC-MS) presenting the storage stability of stilbene glycosides of Norway spruce (Picea abies [L] Karst) bark: fresh bark at sawmill (a); 1-year-stored bark at a sawmill (b); and size exclusion chromatography results of fresh (blue line, unimodal) and 1-year stored bark (red line, bimodal) (c).
Figure 2.
Yield of stilbene glycosides and aglycons in bark of Norway spruce saw logs during storage treatments in winter and summer 2017. The colors of bars indicate the stilbene compounds: green, sum of stilbene glycosides; blue, sum of stilbene aglycones. The whole bark was analyzed without separation into inner and outer layers.
Figure 2.
Yield of stilbene glycosides and aglycons in bark of Norway spruce saw logs during storage treatments in winter and summer 2017. The colors of bars indicate the stilbene compounds: green, sum of stilbene glycosides; blue, sum of stilbene aglycones. The whole bark was analyzed without separation into inner and outer layers.
Figure 3.
Yield of condensed tannins in inner and outer bark of Norway spruce saw logs during storage treatments in winter and summer 2017 as measured by the methods of UV spectrophotometry, λ = 280 nm (a) and high performance liquid chromatography (HPLC) after thiolytic degradation (b).
Figure 3.
Yield of condensed tannins in inner and outer bark of Norway spruce saw logs during storage treatments in winter and summer 2017 as measured by the methods of UV spectrophotometry, λ = 280 nm (a) and high performance liquid chromatography (HPLC) after thiolytic degradation (b).
Figure 4.
Correlation between the results of condensed tannin content analyzed by HPLC and UV methods.
Figure 4.
Correlation between the results of condensed tannin content analyzed by HPLC and UV methods.
Figure 5.
Example of size exclusion chromatogram of samples taken (a) 0-weeks (blue), (b) 4 weeks (red), (c) 12 weeks (green), or (d) 24 weeks (purple) after the onset of storage treatment.
Figure 5.
Example of size exclusion chromatogram of samples taken (a) 0-weeks (blue), (b) 4 weeks (red), (c) 12 weeks (green), or (d) 24 weeks (purple) after the onset of storage treatment.
Figure 6.
The relative distribution of compounds with different molar weights in 70% ethanol (70% EtOH) extracts of inner (a) and outer (b) bark of Norway spruce saw logs during storage treatments during winter and summer 2017 analyzed by HP-SEC. Regions A (yellow), B (blue), and C (green) represent the oligomeric and polymeric structures with molar masses of 15,000–1500 g/mol, 1500–500 g/mol, and 500–50 g/mol, respectively.
Figure 6.
The relative distribution of compounds with different molar weights in 70% ethanol (70% EtOH) extracts of inner (a) and outer (b) bark of Norway spruce saw logs during storage treatments during winter and summer 2017 analyzed by HP-SEC. Regions A (yellow), B (blue), and C (green) represent the oligomeric and polymeric structures with molar masses of 15,000–1500 g/mol, 1500–500 g/mol, and 500–50 g/mol, respectively.
Figure 7.
Relative distribution of oligomeric and polymeric compounds with molar weights of 15,000–1500 g/mol (i.e., region ‘A’ in
Table 4 and
Figure 6) in 70% ethanol (70% EtOH) extracts of Norway spruce saw logs during storage treatments during winter and summer 2017. IB, inner bark; OB, outer bark.
Figure 7.
Relative distribution of oligomeric and polymeric compounds with molar weights of 15,000–1500 g/mol (i.e., region ‘A’ in
Table 4 and
Figure 6) in 70% ethanol (70% EtOH) extracts of Norway spruce saw logs during storage treatments during winter and summer 2017. IB, inner bark; OB, outer bark.
Figure 8.
Oxygen radical absorbance capacity (ORAC; a), ferric ion reducing antioxidant power (FRAP; b), and hydrogen peroxide (H2O2) scavenging activity (SCAV; c) in inner and outer bark of Norway spruce saw logs after 70% ethanol (70% EtOH) extraction during storage treatments during winter and summer in 2017.
Figure 8.
Oxygen radical absorbance capacity (ORAC; a), ferric ion reducing antioxidant power (FRAP; b), and hydrogen peroxide (H2O2) scavenging activity (SCAV; c) in inner and outer bark of Norway spruce saw logs after 70% ethanol (70% EtOH) extraction during storage treatments during winter and summer in 2017.
Figure 9.
Oxygen radical absorbance capacity (ORAC) of Norway spruce bark (saw logs) as a function of total amounts of condensed tannins and stilbenes (a) and stilbene glycosides and aglycones (b) as analyzed by HPLC, UV and GC-MS methods during storage treatments in 2017.
Figure 9.
Oxygen radical absorbance capacity (ORAC) of Norway spruce bark (saw logs) as a function of total amounts of condensed tannins and stilbenes (a) and stilbene glycosides and aglycones (b) as analyzed by HPLC, UV and GC-MS methods during storage treatments in 2017.
Figure 10.
Single-stem set-up of storage experiment in winter (a) and summer (b) in 2017.
Figure 10.
Single-stem set-up of storage experiment in winter (a) and summer (b) in 2017.
Figure 11.
Monthly mean, minimum and maximum air temperatures (i.e., low, average, high, respectively) and monthly precipitation sum at the site during the experiment in winter and summer 2017.
Figure 11.
Monthly mean, minimum and maximum air temperatures (i.e., low, average, high, respectively) and monthly precipitation sum at the site during the experiment in winter and summer 2017.
Figure 12.
Experimental setup of single stem logs in storage experiment (a), and schematic presentation of the bark sampling from individual saw logs (b) and pulpwoods (c) for chemical and antioxidative analysis.
Figure 12.
Experimental setup of single stem logs in storage experiment (a), and schematic presentation of the bark sampling from individual saw logs (b) and pulpwoods (c) for chemical and antioxidative analysis.
Table 1.
Results (p-values) from testing the statistical differences between storage time (i.e., weeks after the treatment onset), season (i.e., winter and summer 2017), and the layers within bark (i.e., inner and outer bark) in terms of the quantitative amounts of stilbene glycosides and aglycones, condensed tannins analyzed with HPLC and spectrophotometric methods (CTs HPLC, CTs UV); and the analysis of antioxidative activities of bark extracts (70% EtOH) of Norway spruce saw logs analyzed with ORAC, FRAP, and SCAV tests. Interaction terms are indicated by x.
Table 1.
Results (p-values) from testing the statistical differences between storage time (i.e., weeks after the treatment onset), season (i.e., winter and summer 2017), and the layers within bark (i.e., inner and outer bark) in terms of the quantitative amounts of stilbene glycosides and aglycones, condensed tannins analyzed with HPLC and spectrophotometric methods (CTs HPLC, CTs UV); and the analysis of antioxidative activities of bark extracts (70% EtOH) of Norway spruce saw logs analyzed with ORAC, FRAP, and SCAV tests. Interaction terms are indicated by x.
| p-Values, Saw Logs | |
---|
Factor | Stilbene Glycosides | Stilbene Aglycones | CTs HPLC | CTs UV | ORAC | FRAP | SCAV |
---|
Storage time | 0.003 | 0.007 | 0.005 | 0.000 | 0.001 | 0.000 | 0.031 |
Bark layer | n.d. | n.d. | 0.000 | 0.000 | 0.001 | 0.001 | 0.025 |
Season | 0.009 | 0.010 | 0.140 | 0.052 | 0.526 | 0.386 | 0.275 |
Storage time × Bark layer | n.d. | n.d. | 0.001 | 0.003 | 0.145 | 0.002 | 0.465 |
Storage time × Season | n.d. | n.d. | 0.061 | 0.152 | 0.089 | 0.006 | 0.737 |
Bark layer × Season | n.d. | n.d. | 0.003 | 0.001 | 0.177 | 0.287 | 0.543 |
Storage time × Bark layer × Season | n.d. | n.d. | 0.021 | 0.030 | 0.730 | 0.399 | 0.563 |
Table 2.
Composition and properties of proanthocyanidins in Norway spruce bark (saw logs) samples during the storage treatments in winter and summer 2017.
Table 2.
Composition and properties of proanthocyanidins in Norway spruce bark (saw logs) samples during the storage treatments in winter and summer 2017.
Season | Time Weeks | Sample | DP 1 | PC 2 (%) | PD 3 (%) | A-type 4 (%) |
---|
W | 0 | IB | 8.2 ± 0.7 | 100.0 | n.d. | n.d. |
W | 2 | IB | 8.7 ± 0.8 | 100.0 | n.d. | n.d. |
W | 4 | IB | 7.4 ± 1.0 | 99.9 | 0.2 | n.d. |
W | 12 | IB | 8.0 ± 1.8 | 100.0 | n.d. | n.d. |
W | 24 | IB | 8.3 ± 2.8 | 95.5 | 4.5 | n.d. |
W | 0 | OB | 6.1 ± 0.4 | 83.4 | 16.6 | 1.5 |
W | 2 | OB | 6.4 ± 0.4 | 90.5 | 9.5 | n.d. |
W | 4 | OB | 6.2 ± 0.8 | 83.8 | 16.2 | n.d. |
W | 12 | OB | 6.9 ± 1.8 | 84.8 | 14.2 | n.d. |
W | 24 | OB | 6.6 ± 0.4 | 86.0 | 14.1 | 1.3 |
S | 0 | IB | 7.1 ± 0.1 | 100.0 | n.d. | 2.8 |
S | 2 | IB | 5.6 ± 0.6 | 99.2 | 1.6 | 5.6 |
S | 4 | IB | 6.2 ± 0.7 | 100.0 | n.d. | 3.6 |
S | 12 | IB | 8.0 ± 0.4 | 97.1 | 2.9 | 2.2 |
S | 24 | IB | 6.2 ± 0.3 | 95.2 | 4.8 | n.d. |
S | 0 | OB | 5.9 ± 0.4 | 93.6 | 6.5 | 2.6 |
S | 2 | OB | 5.5 ± 0.6 | 91.2 | 8.8 | 2.7 |
S | 4 | OB | 7.0 ± 0.2 | 80.4 | 19.7 | 1.6 |
S | 12 | OB | 7.5 ± 0.5 | 84.1 | 16.0 | n.d. |
S | 24 | OB | 6.7 ± 0.1 | 81.7 | 18.3 | n.d. |
Table 3.
Results (p-values) from testing the statistical differences between storage time (i.e., weeks after the treatment onset), season (i.e., winter and summer 2017), and the layers within bark (i.e., inner and outer bark) in terms of relative distribution of compounds with different molar weights in 70% ethanol (70% EtOH) extracts of Norway spruce saw logs during storage treatments in winter and summer 2017 analyzed with HP-SEC. Regions A, B, and C represent the oligomeric and polymeric structures with molar masses of 15,000–1500 g/mol, 1500–500 g/mol, and 500–50 g/mol, respectively. Interaction terms are indicated by x.
Table 3.
Results (p-values) from testing the statistical differences between storage time (i.e., weeks after the treatment onset), season (i.e., winter and summer 2017), and the layers within bark (i.e., inner and outer bark) in terms of relative distribution of compounds with different molar weights in 70% ethanol (70% EtOH) extracts of Norway spruce saw logs during storage treatments in winter and summer 2017 analyzed with HP-SEC. Regions A, B, and C represent the oligomeric and polymeric structures with molar masses of 15,000–1500 g/mol, 1500–500 g/mol, and 500–50 g/mol, respectively. Interaction terms are indicated by x.
| p-Values, Saw Logs |
---|
Factor | A | B | C |
---|
Storage time | 0.002 | 0.568 | 0.143 |
Bark layer | 0.001 | 0.002 | 0.138 |
Season | 0.337 | 0.141 | 0.257 |
Storage time × Bark layer | 0.059 | 0.192 | 0.382 |
Storage time × Season | 0.171 | 0.279 | 0.248 |
Bark layer × Season | 0.186 | 0.540 | 0.350 |
Storage time × Bark layer × Season | 0.452 | 0.225 | 0.257 |
Table 4.
Results (p-values) from testing the statistical differences between storage time (i.e., weeks after the treatment onset), season (i.e., winter and summer 2017), and the layers within bark (i.e., inner and outer bark) in antioxidative activities of bark extracts (70% EtOH) of Norway spruce pulpwood logs analyzed with ORAC, FRAP, and SCAV tests. Interaction terms are indicated by x.
Table 4.
Results (p-values) from testing the statistical differences between storage time (i.e., weeks after the treatment onset), season (i.e., winter and summer 2017), and the layers within bark (i.e., inner and outer bark) in antioxidative activities of bark extracts (70% EtOH) of Norway spruce pulpwood logs analyzed with ORAC, FRAP, and SCAV tests. Interaction terms are indicated by x.
| p-Values, Pulpwood |
---|
Factor | ORAC | FRAP | SCAV |
---|
Storage time | 0.000 | 0.000 | 0.018 |
Bark layer | 0.323 | 0.225 | 0.006 |
Season | 0.014 | 0.001 | 0.399 |
Storage time × Bark layer | 0.644 | 0.357 | 0.412 |
Storage time × Season | 0.001 | 0.546 | 0.052 |
Bark layer × Season | 0.765 | 0.577 | 0.043 |
Storage time × Bark layer × Season | 0.421 | 0.452 | 0.385 |
Table 5.
Tree ages and dimensions of saw log samples of the storage studies. Samples from two stems were taken each sampling time.
Table 5.
Tree ages and dimensions of saw log samples of the storage studies. Samples from two stems were taken each sampling time.
| Storage Sample | Sampling Date | Storage Time | Tree Age | Tree Height | D1.3 m | Log Length | Log Diameter |
---|
Butt End | Middle | Top |
---|
| Number | | Weeks | Years | dm | mm | mm | dm | mm | mm | mm | mm | mm | mm |
---|
Winter Storage | 3 | 7.2.2017 | 0 | 119 | 225 | 362 | 345 | 47 | 310 | 319 | 290 | 306 | 261 | 270 |
33 | 7.2.2017 | 0 | 96 | 223 | 321 | 272 | 46 | 273 | 255 | 242 | 249 | 215 | 227 |
12 | 21.2.2017 | 2 | 95 | 221 | 282 | 291 | 45 | 257 | 275 | 235 | 251 | 221 | 223 |
15 | 21.2.2017 | 2 | 110 | 222 | 323 | 345 | 46 | 302 | 291 | 293 | 277 | 255 | 243 |
1 | 7.3.2017 | 4 | 97 | 210 | 301 | 299 | 47 | 260 | 258 | 234 | 238 | 216 | 219 |
2 | 7.3.2017 | 4 | 94 | 215 | 280 | 277 | 46 | 282 | 279 | 257 | 263 | 235 | 232 |
30 | 2.5.2017 | 12 | 73 | 206 | 260 | 263 | 46 | 234 | 226 | 204 | 207 | 191 | 185 |
34 | 2.5.2017 | 12 | 56 | 213 | 362 | 362 | 45 | 317 | 305 | 282 | 290 | 254 | 262 |
14 | 25.7.2017 | 24 | 96 | 224 | 323 | 341 | 46 | 264 | 269 | 238 | 244 | 207 | 210 |
31 | 25.7.2017 | 24 | 78 | 256 | 305 | 299 | 46 | 282 | 281 | 256 | 261 | 247 | 240 |
Summer Storage | 41 | 30.5.2017 | 0 | 67 | 243 | 307 | 310 | 48 | 279 | 272 | 262 | 254 | 243 | 237 |
51 | 30.5.2017 | 0 | 70 | 245 | 362 | 357 | 44 | 310 | 311 | 300 | 291 | 292 | 289 |
47 | 12.6.2017 | 2 | 84 | 259 | 360 | 345 | 44 | 300 | 292 | 287 | 285 | 273 | 265 |
50 | 12.6.2017 | 2 | 108 | 233 | 317 | 327 | 47 | 272 | 287 | 251 | 249 | 232 | 219 |
44 | 26.6.2017 | 4 | 100 | 270 | 392 | 399 | 43 | 350 | 342 | 324 | 326 | 313 | 305 |
49 | 26.6.2017 | 4 | 95 | 255 | 360 | 364 | 49 | 303 | 310 | 281 | 284 | 254 | 256 |
45 | 22.8.2017 | 12 | 94 | 260 | 326 | 326 | 47 | 284 | 290 | 274 | 267 | 290 | 246 |
46 | 22.8.2017 | 12 | 58 | 225 | 304 | 300 | 48 | 256 | 239 | 225 | 219 | 206 | 199 |
42 | 13.11.2017 | 24 | 89 | 262 | 359 | 358 | 46 | 329 | 318 | 316 | 305 | 290 | 284 |
43 | 13.11.2017 | 24 | 93 | 252 | 285 | 278 | 48 | 271 | 260 | 246 | 242 | 226 | 224 |
Table 6.
Tree ages and dimensions of pulpwood samples of the storage studies. Samples from two stems were taken each sampling time.
Table 6.
Tree ages and dimensions of pulpwood samples of the storage studies. Samples from two stems were taken each sampling time.
| Storage Sample | Sampling Date | Storage Time | Tree Age | Tree Height | D1.3 m | Log Length | Log Diameter |
---|
Butt End | Middle | Top |
---|
| Number | | Weeks | Years | dm | mm | mm | dm | mm | mm | mm | mm | mm | mm |
---|
Winter Storage | 22 | 7.2.2017 | 0 | 69 | 114 | 121 | 124 | 46 | 133 | 143 | 113 | 113 | 98 | 97 |
23 | 7.2.2017 | 0 | 65 | 124 | 127 | 131 | 50 | 136 | 146 | 119 | 125 | 102 | 103 |
8 | 21.2.2017 | 2 | 103 | 114 | 132 | 125 | 48 | 152 | 145 | 122 | 120 | 97 | 97 |
29 | 21.2.2017 | 2 | 38 | 129 | 151 | 145 | 50 | 153 | 160 | 145 | 136 | 110 | 110 |
10 | 7.3.2017 | 4 | 86 | 142 | 155 | 153 | 50 | 177 | 175 | 149 | 152 | 130 | 125 |
16 | 7.3.2017 | 4 | 82 | 125 | 126 | 129 | 51 | 150 | 150 | 120 | 122 | 103 | 103 |
18 | 2.5.2017 | 12 | 81 | 121 | 129 | 121 | 51 | 180 | 157 | 120 | 115 | 100 | 109 |
25 | 2.5.2017 | 12 | 50 * | 130 | 130 | 137 | 53 | 153 | 155 | 130 | 129 | 104 | 108 |
4 | 25.7.2017 | 24 | 87 | 143 | 139 | 140 | 48 | 150 | 153 | 133 | 131 | 118 | 118 |
27 | 25.7.2017 | 24 | 49 | 114 | 136 | 137 | 51 | 143 | 144 | 126 | 129 | 105 | 101 |
Summer Storage | 54 | 30.5.2017 | 0 | 90 | 117 | 147 | 134 | 51 | 165 | 195 | 134 | 137 | 106 | 109 |
56 | 30.5.2017 | 0 | 87 | 112 | 119 | 131 | 52 | 141 | 145 | 121 | 120 | 93 | 92 |
58 | 12.6.2017 | 2 | 62 | 121 | 125 | 119 | 51 | 143 | 140 | 113 | 108 | 90 | 91 |
59 | 12.6.2017 | 2 | 55 | 100 | 124 | 124 | 52 | 144 | 143 | 112 | 109 | 75 | 79 |
55 | 26.6.2017 | 4 | 85 | 130 | 157 | 155 | 55 | 184 | 184 | 154 | 143 | 126 | 121 |
61 | 26.6.2017 | 4 | 70 | 128 | 145 | 137 | 53 | 132 | 136 | 119 | 120 | 98 | 96 |
53 | 22.8.2017 | 12 | 70 | 127 | 164 | 162 | 51 | 187 | 199 | 159 | 157 | 135 | 136 |
60 | 22.8.2017 | 12 | 56 | 127 | 147 | 144 | 47 | 186 | 176 | 139 | 143 | 124 | 124 |
52 | 13.11.2017 | 24 | 79 | 134 | 158 | 170 | 51 | 202 | 193 | 157 | 150 | 132 | 135 |
57 | 13.11.2017 | 24 | 98 | 153 | 145 | 144 | 51 | 165 | 163 | 140 | 130 | 124 | 115 |