## 3 Results and Discussion
### Huanglongbing Effects on the Volatile Profile of \"Ray Ruby\" Grapefruit Peel Oil
** & **VOC** & \multicolumn{2}{c}{**Calculated**} & \multicolumn{2}{c}{**Reference**} & \multicolumn{4}{c}{**2020**} & \multicolumn{2}{c}{**2021**} \\  & & **RI \({}^{\pm}\)** & **RI \({}^{\pm}\)** & **HLB\({}^{\pm}\)** & **HLB\({}^{\pm}\)** & **\(P\)-Value** & **Difference\({}^{\pm}\)** & **HLB\({}^{-}\)** & **HLB\({}^{\pm}\)** & **\(P\)-Value** & **Difference** \\ \hline
44 & Unfactual & 1307 & 1305 & 0.018 & 0.018 & 0.011 & 0.1639 & \(-\)44.407s & 0.014 & 0.012 & 0.02492 & \(-\)14.307s \\
45 & Dehandle acid & 1351 & 1300 & 0.007 & 0.018 & 0.0411 & \(-\)57.00s & 0.017 & 0.002 & 0.03734 & \(-\)2.507s \\
47 & \({}^{\prime}\)(Z)-primordial acute & 1362 & 1360 & 0.017 & 0.018 & 0.0491 & 5.90s & 0.016 & 0.024 & 0.1349 & 5.007s \\
48 & \({}^{\prime}\)(Z)-primordial acute & 1369 & 1361 & 0.007 & 0.009 & 0.0546 & 2.860s & 0.006 & 0.009 & 0.03138 & 5.007s \\
49 & \({}^{\prime}\)(CamCam) acetate & 1377 & 1380 & 0.083 & 0.062 & 0.0141 & \(-\)25.30s & 0.084 & 0.074 & 0.4158 & -11.907s \\
50 & Ethly decanoate & 1367 & 1391 & 0.002 & 0.001 & 0.0190 & \(-\)50.00s & 0 & 0 & 0.0181 & \(-\)20.903s \\
51 & \({}^{\prime}\)(A-Cepene) & 1402 & 1380 & 0.151 & 0.197 & 0.0175 & \(-\)30.50s & 0.134 & 0.162 & 0.0181 & \(-\)20.903s \\
52 & Dehaççal & 1407 & 1405 & 0.102 & 0.014 & 0.0671 & \(-\)20.00s & 0.024 & 0.0682 & \(-\)4.007s \\
53 & \({}^{\prime}\)(A-Cepene)-86.36 & 1443 & 1426 & 0.138 & 0.172 & 0.0149 & \(-\)26.50s & 0.224 & 0.146 & 0.0224 & \(-\)20.207s \\
54 & \({}^{\prime}\)(A-Cepene)-86.36 & 1443 & 1426 & 0.136 & 0.017 & 0.0194 & \(-\)26.50s & 0.226 & 0.146 & 0.0224 & \(-\)20.207s \\
55 & \({}^{\prime}\)(A-Cepene)-86.36 & 1452 & 1420 & 0.142 & 0.0151 & 0.0257 & \(-\)21.60s & 0.036 & 0.046 & 0.0589 & 5.620s \\
56 & \({}^{\prime}\)(Z-P)-Japanese & 1457 & 1443 & 0.012 & 0.017 & 0.2491 & \(-\)21.07s & 0.015 & 0.025 & 0.0485 & 31.645s \\
57 & \({}^{\prime}\)(A-Cepene) & 1400 & 1400 & 0.005 & 0.006 & 0.0741 & \(-\)20.00s & 0.005 & 0.007 & 0.0081 & 40.007s \\
58 & \({}^{\prime}\)(A-Cepene) & 1462 & 1440 & 0.005 & 0.006 & 0.0719 & \(-\)20.00s & 0.005 & 0.007 & 0.0080 & 40.007s \\
59 & \({}^{\prime}\)(A-Humandez) & 1489 & 1455 & 0.064 & 0.076 & 0.1021 & \(18.80\)s & 0.047 & 0.066 & 0.0221 & \(-\)40.407s \\
60 & \({}^{\prime}\)(A-Mununetene) & 1502 & 1477 & 0 & 0.01 & 0.0001 & \(+\) & 0.008 & 0.009 & 0.006 & \(-\)80.006 & 50.007s \\
61 & \({}^{\prime}\)(A-Frames) & 1508 & 1506 & 0.011 & 0.023 & 0.0657 & \(19.10\)s & 0.0 & 0 & 0.0290 & \(-\)25.007s \\
62 & \({}^{\prime}\)(Cepene) D & 1515 & 14827319 & 0.087 & 0.1038 & 0.288 & \(38.90\)s & 0.083 & 0.079 & \(-\)25.007s \\
63 & \({}^{\prime}\)(A-Munetene) & 1513 & 1500 & 0.024 & 0.028 & 0.7341 & \(38.30\)s & 0.014 & 0.02 & 0.028 & \(-\)25.007s \\
64 & \({}^{\prime}\)(A-Munetene) & 1553 & 1510 & 0.003 & 0.004 & 0.06 & \(33.30\)s & 0.003 & 0.009 & 0.0583 & \(-\)20.007s \\
65 & \({}^{\prime}\)(B-Sapphire)-Lunderer & 1540 & 1521 & 0 & 0 & 0 & 0 & 0 & 0 & 0.0036 & \(-\)4.0 \\
67 & \({}^{\prime}\)(A-Cepene) & 1547 & 1523 & 0.177 & 0.211 & 0.0179 & \(-\)19.20s & 0.148 & 0.184 & 0.0455 & \(-\)24.303s \\
68 & \({}^{\prime}\)(L-Navrido) & 1570 & 1553 & 0.028 & 0.017 & 0.0191 & \(-\)39.30s & 0.090 & 0.091 & 0.031 & \(-\)39.110s \\
69 & \({}^{\prime}\)(E) & 1557 & 1551 & 0.041 & 0.045 & 0.0594 & \(9.80\)s & 0.022 & 0.025 & 0.0168 & \(-\)16.070s \\
70 & \({}^{\prime}\)(Cepepylene oxide) & 1600 & 1580 & 0.024 & 0.017 & 0.1633 & \(-\)20.20s & 0.012 & 0.011 & 0.1337 & \(-\)3.307s \\
71 & \({}^{\prime}\)(F-Eastrand) & 1675 & 1622 & 0 & 0.088 & 0.0138 & \(-\)4.1 & 0.005 & 0.005 & 0.0573 & 0.007s \\
72 & \({}^{\prime}\)(A-Cepene) & 1696 & 1625 & 0.099 & 0.012 & 0.1668 & \(33.30\)s & 0.017 & 0.027 & 0.027 & \(-\)0.007s \\
74 & \({}^{\prime}\)(B-S-Smeal) & 1719 & 1706 & 0.02 & 0.025 & 0.2684 & \(30.00\)s & 0.017 & 0.023 & 0.413 & \(35.30\)s \\
75 & \({}^{\prime}\)(Navrido) & 1843 & 1820 & 0.127 & 0.016 & 0.0284 & \(-\)57.04s & 0.019 & 0.007 & 0.0099 & \(-\)63.027s \\ \hline \multicolumn{10}{c}{Figure 3: Combined cluster analysis and heat map of grapefruit peel oil samples from healthy (HLB\(-\)) and HLB-affected fruits (HLB+) from 2020 (HLB\(-\) 20 and HLB+ 20) and 2021 (HLB\(-\) 21 and HLB+ 21) harvests (columns) and identified VOCs (rows).