In this answer, I am assuming that you want to keep correlations constant.
To begin with, note that the $N\times N$ covariance matrix $\Sigma$ with element $\Sigma_{i,j}=Cov(x_i,x_j)$ can be written as
$$
\Sigma = \mathbf{SRS}
$$
where $\mathbf{S}$ is a diagonal matrix of the simple volatilties $\sigma_i$, and $\mathbf{R}$ is the correlation matrix. Thus in a matrix sense,
$$
\frac{\partial \mathbf{\Sigma}}{\partial\sigma_i}=\frac{\partial\mathbf{SRS}}{\partial\sigma_i}=\frac{\partial\mathbf{S}}{\partial\sigma_i}\mathbf{RS}+\mathbf{SR}\frac{\partial\mathbf{S}}{\partial\sigma_i}
$$
The derivative of $\mathbf{S}$ with respect to $\sigma_i$ is a diagonal matrix of zeros, whose $i$th element is $1$. It is a single-entry matrix or a selector matrix, which we shall denote $\mathbf{E}_i$. For example, for $\mathbf{E}_2$ is
$$
\mathbf{E}_2=\begin{pmatrix}0&0&0&\ldots &0\\
0&1&0&\ldots &0\\
\ldots &\ldots &\ldots &\ldots &\ldots \\
0&0&0&\ldots &0\\\end{pmatrix}
$$
Hence,
$$
\frac{\partial\mathbf{\Sigma}}{\partial\sigma_i}=\mathbf{E}_i\mathbf{RS}+\mathbf{RS}\mathbf{E}_i
$$
Thus, the marginal impact of a change in (any) of the volatilities on portfolio variance $v=\mathbf{w}^T\mathbf{\Sigma} \mathbf{w}$ can be computed as (after some algebra)
$$
\frac{\partial v}{\partial \mathrm{diag(S)}}=\mathbf{w}^T\frac{\partial \mathbf{\Sigma}}{\partial \mathrm{diag(S)}}\mathbf{w}=2\mathbf{w}\otimes \left(\mathbf{RSw}
\right)$$
where $\otimes$ denotes element wise multiplication, i.e. $x\otimes y = \mathrm{diag}(xy^T)$. Conveniently, this formulation returns all derivatives at once.
Example: With
$$
\mathbf{S}=\mathrm{diag}\begin{pmatrix}0.1&0.2&0.3\end{pmatrix}
$$
and
$$
\mathbf{R}=\begin{pmatrix}1 & 0.5 & 0.25 \\ 0.5 & 1 & 0.1 \\ 0.25 & 0.1 & 1\end{pmatrix}
$$
and a weight vector
$$
\mathbf{w}=\begin{pmatrix}0.2 & 0.3 & 0.5\end{pmatrix}^T
$$
we find
$$
\frac{\partial v}{\partial \mathrm{diag(S)}}=2\mathbf{w}\otimes \left(\mathbf{RSw}
\right)=2\begin{pmatrix}.2\\.3\\.5\end{pmatrix}\otimes\begin{pmatrix}0.0875\\0.085\\0.161\end{pmatrix}=\begin{pmatrix}0.035\\0.051\\0.161\end{pmatrix}
$$
Thus, for example, the sensitivity of the portfolio variance with respect to the first volatility is 0.035.
With a bit more of algebra, you can find the impact of standalone vols on any portfolio optimisation solution, e.g. the MVP. Using the results from above and the fact that $\sigma_{MVP}=\frac{1}{\mathbf{1}^T{\Sigma^{-1} 1}}$ and the knowledge that $\mathbf{\Sigma}^{-1}=\mathbf{S}^{-1}\mathbf{R}^{-1}\mathbf{S}^{-1}$.