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We present the results of a spectroscopic analysis of extremely strong damped Lyman-α absorbers (ESDLAs, log N(Hi)>=21.7) observed with VLT-XShooter. ESDLAs probe gas from within the star-forming disk of the associated galaxies and thus ESDLAs provide a unique opportunity to study the interstellar medium of galaxies at high-redshift. We report column densities (N), equivalent widths (w), and the kinematic spread (Δ v90) of species from neutral, singly ionised, and higher ionisation species. We find that, using the dust correction prescription, the measured metallicities are consistent for singly ionised gas species such as Pii, S ii, Si ii, Mnii and Crii, and Znii in all ESDLAs within 3-sigma uncertainty. We find that the distributions of N(Ari)/N(Hi) ratio in DLAs and ESDLAs are similar. We further report that ESDLAs do not show a strong deficiency of Ari relative to other α-capture elements as is seen in DLAs. This supports the idea that the mentioned under-abundance of Ari in DLAs is possibly caused by the presence of background UV photons that penetrate the low N(Hi) clouds to ionise Ari, but they cannot penetrate deep enough in the high N(Hi) ESDLA environment. The w(Mgii lambda2796) distribution in ESDLAs is found to be similar to that of metal-rich Ci-selected absorbers, but the velocity spread of their Mgii profile is different. For higher ionisation species (such as C iv and Si iv), Δ v90 is similar in the two populations, while the Δ v90 of singly ionised species is smaller for ESDLAs. This suggests that the ESDLAs sample a different Hi region of their associated galaxy compared to the general DLA population. We further study the N(Cl i) distribution in high-redshift DLA and ESDLA sightlines, as Cl i is a good tracer of H2 gas. The N(Cl i)-N(H2) correlation is followed by all the clouds (ESDLAs and otherwise) having log N(H2)<22.