Eight provenances [two (P1 & P2) falling in Satpura mountain ranges and six (P3 & P8) in northern most tip of western Ghats or Sahyadri mountain ranges] were selected in Gujarat, India (Table 1). Sagai-1 and Sagai-2, provenances area characterized by black cotton soils, with average (30 years) annual normal rainfall of 924.8 mm and average annual maximum and minimum temperature of 34.7℃ and 20.7℃, respectively. Nanaponda and Kaprada provenances, a northern extension of Central Indian Deccan Plateau, belong to late Cretaceous-early Eocene age and followed by Quaternary sediments, have black cotton soils. The maximum daily temperature ranges from 32.2℃ to 41.2℃ while minimum temperature from 9.9℃ to 23.3℃. Average annual rainfall in these provenances is 2399 mm and 2842 mm, respectively. Waghai and Chichinagavtha, and Mahal and Ahwa provenances fall under south and north Dangs region, respectively. These areas have black rock-outcrops, shallow black, brown and alluvial soils of recent origin. The average annual rainfall ranges from 1500 to 3000 mm and average annual temperature is about 26℃ and maximum temperature may shoot up to 46ºC and the winter temperatures 22℃.

Five trees (each tree representing one replication) were selected randomly from each provenance for leaf fodder sample collection. Tree growth parameters viz. tree height and diameter at breast height (DBH) and average canopy area (m2) were recorded (Table 1). Leaf samples were collected from all directions (north-south and east-west) at lower, middle and upper tree canopy. The samples were washed with distilled water in laboratory and air-dried followed by drying in oven at 60℃±5℃ till constant weight was achieved. The dried samples were then finely grounded (particle size<1 mm) using grinder and laboratory grade pulverizer. Volatile and non-volatile compounds were estimated for winter and summer seasons of 2020 and 2021 and averaged to ascertain the provenance and seasonal variations.

M. dubia leaf sample phytochemicals were detected through Gas-chromatography mass-spectrometry (GC-MS) following Murugesan et al. (2013).

Non targeted gas-chromatography mass-spectrometry (GC-MS) analysis of M. dubia leaf samples of different provenances and seasons i.e. winter (S1) and summer (S2) seasons, revealed an array of 93 volatile phytochemicals (Table 2). Chromatograms (randomly selected 4 out of 16 chromatograms of 8 provenances and two seasons) showing peak area and retention time of detected phytochemicals are depicted in figure 1 to 4 Total 76 and 60 compounds were detected in winter 1. and summer, respectively (Table 3). Maximum of 55 and 35 compounds in winter and summer sample, respectively, were detected from Sagai-2 (P2 ) provenance. The lowest (23) compounds were detected in Chichinagavtha provenance (P6) in winter and summer. As many as, 43 common phytochemicals (Table 3) numbered 5, 7, 9, 13, 17, 19, 20, 23, 24, 26, 27, 30, 35, 36, 40, 45, 46, 47, 49, 52, 53, 55, 57, 60, 61, 62, 63, 64, 65, 69, 70, 73, 74, 76,77, 80, 81, 82, 85, 88, 89, 92 and 93 were identified in winter and summer season. Whereas, 33 phytochemicals numbered 4, 8,10, 11, 12, 14, 18, 22, 28, 29, 32, 33, 34, 38, 39, 41, 42,43, 44, 50, 54, 56, 59, 66, 67, 71, 75, 78, 83, 84, 86, 87 and 90 were only detected in winter. Similarly, 17 phytochemicals numbered 1, 2, 3, 6, 15, 16, 21, 25, 31,37, 48, 51, 58, 68, 72, 79 and 91 were unique in summer (Table 3).

Comparison of per cent peak area (Table 3) revealed that l-(+)-Ascorbic acid 2,6-dihexadecanoate; Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1); dl-a-Tocopherol; 2,4-Di-tert-butylphenol; 3,7,11,15- Tetramethyl-2-hexadecen-1-ol; Neophytadiene; 9,12,15-Octadecatrienoic acid, (Z,Z,Z)-; 2- Dimethyl(ethenyl)silyloxytetradecane; Sebacic acid, di(2-propylpentyl) ester; 2,3-Dimethyl-3-pyrazolin- 5- one; 2- Propenoic acid, 2-( acetylamino)-; Nonadecane, 2-methyl-; 4-Heptanol, 2,6-dimethyl-4- (1-methylethyl)-; 1-Hexadecanol; 9-Nonadecene; Octadecanoic acid; Eicosane, 2-methyl-; 10- Heneicosene (c,t); 2-Pentadecanone, 6,10,14- trimethyl-; D-Mannitol, 1,2:3,4:5,6-tris-O-(1- methylethylidene)- were found in higher concentration (decreasing order) in winter and summer, respectively.

Paritala et al. (2015) reported that different members of Meliaceae family such as A. indica and M. dubia possess a vast array of biologically active compounds which are chemically diverse and structurally complex. Earlier, Parmar et al. (2019) reported 18 different types of phytochemicals in M. dubia leaf through GC–MS analysis. Murugesan et al. (2013) reported 42 phytochemicals from the M. dubia leaf. J a h i r h u s s a i n e t a l . ( 2 0 1 5 ) i d e n t i f i e d 3 3 phytochemicals as constituents with more than one peak area for 7 compounds from ethanolic leaf extract of M. composita. Mudhafar et al. (2020) reported 22 phytochemical compounds from M. dubia leaves using GCMS analysis. Our GC-MS analysis revealed greater number of phytochemicals as compared to previous reports on this species. The results deduced that there was variation in phytochemical compound occurrence among provenances and seasons. Synthesis of chemical compounds within plant system happens in response to external environmental stimuli caused by edapho-climatic stresses. It could be also be due to biotic stimuli (insect pest attack) to which plant develop defence and compounds synthesized could be beneficial for human beings and wild and domestic animals feeding on it (Tekli´c et al., 2021; Sukhadiya et al., 2022).

Corroboration of chemical compounds detected in our study with available literature revealed that they occur in other species of same family (Balasubramanian et al., 2014; Kumar et al., 2018) and have one or the other beneficial biological activities. The most common are anti-bacterial, anti-inflammatory agent, antioxidant, insecticidal, analgesic, antipyretic, antiarthritic, a n t i c a n c e r , a n t i h i s t a m i n i c , a n t i e c z e m i c , antiandrogenic, hypo-cholesterolemic, antiviral anxiolytic activity etc. Many of them are used to cure gum disease and skin infections and other ailments (Wang and Huang, 2012; Hamid et al., 2016; Ruthisha et al., 2017; Gravel et al., 2017; Swamy et al., 2017; Amudha et al., 2018; Elgorban et al., 2019; Zhao et al., 2020; Bratty et al., 2020; Chikezie et al., 2020; Subramanian et al., 2020; Prodhan and Mridu, 2021; Huang et al., 2021; Sethuraman and Ramachandran 2022; Moussaoui et al., 2022). Thus, M. dubia leaf volatile phytochemicals are biologically active compounds and the leaf fodder could beneficial as top feed for livestock.

The presence of volatile compounds in M. dubia leaf could be source antioxidant, anti-inflammatory, and antibacterial activity etc. (Diaz-Sanchez et al., 2015; Kumar and Goel, 2019; Wong et al., 2020). And its feeding to small ruminants and livestock may have positive effect toward animals in terms of favored growth performance, production quality, and enhanced endogenous antioxidant systems, possibly by directly affecting specific molecular targets or/and indirectly as stabilized conjugates affecting the metabolic pathways (Hamaker et al., 2009; Jorgensen et al., 2010; Wong et al., 2020). Alkaloids have antibacterial activity which could be beneficial to livestock. Achi et al. (2017) reported that flavonoids (1.36%) present in Ficus capensis leaves possess medicinal benefits which includes antioxidant and

anti-inflammatory activity. Saponins of plant origins are important dietary supplements and exhibit antimicrobial activities and protect plants from microbial pathogens. Tree leaves show high digestibility values associated with low TTC levels (Forwood and Owensby, 1985). Total tannin content range of M. dubia leaf in present study fall within the values (0.89 to 30.43%) reported in other top feed species (Niranjan et al., 2007; Datt et al., 2008; Wankhede and Jain, 2011; Achi et al., 2017). TTC values of M. dubia leaf also fall within the range advocated suitable in livestock feed (Devasena and Adilaxmamma, 2016).

Table 1. Geographical location of M. dubia provenances (P1-P2 in Satpura mountain ranges and P3 -P8 in The Northern most Western Ghats or Sahyadri mountain ranges) in Gujarat India, selected in the study

Table 2. M. dubia leaf volatile phytochemicals detected using non targeted gas chromatography mass spectrometry (GC-MS)