Suppose that, in this question, the principal value of the argument is chosen to be the unique value of the argument that lies within the interval $(−\pi,\pi]$. Then, since, for any $z$ for which $\arg(z\pm i)$ are defined, $\arg(z-i)-\arg(z+i)\lt\frac{\pi}{2}$ holds, there is no $z$ such that $\arg(z-i)-\arg(z+i)=\frac{2\pi}{3}$ (for the details, see the end of this answer).
This suggests that the question defines the range of the principal value as being in the closed-open interval $[0, 2\pi)$.
Let $z=x+yi$ where $x,y\in\mathbb R$.
Then, we have
$$\arg(x+yi)=\begin{cases}2\pi-\arctan(\frac{-y}{x})&\text{if $x\gt 0$ and $y\lt 0$}
\\\arctan(\frac yx)&\text{if $x\gt 0$ and $y\geqslant 0$}
\\\frac{3}{2}\pi&\text{if $x=0$ and $y\lt 0$}
\\\text{undefined}&\text{if $x=0$ and $y=0$}
\\\frac{\pi}{2}&\text{if $x=0$ and $y\gt 0$}
\\\pi+\arctan(\frac{-y}{-x})&\text{if $x\lt 0$ and $y\leqslant 0$}
\\\pi-\arctan(\frac{y}{-x})&\text{if $x\lt 0$ and $y\gt 0$}
\end{cases}$$
i.e.
$$\arg(x+yi)=\begin{cases}2\pi+\arctan(\frac{y}{x})&\text{if $x\gt 0$ and $y\lt 0$}
\\\arctan(\frac yx)&\text{if $x\gt 0$ and $y\geqslant 0$}
\\\frac{3}{2}\pi&\text{if $x=0$ and $y\lt 0$}
\\\text{undefined}&\text{if $x=0$ and $y=0$}
\\\frac{\pi}{2}&\text{if $x=0$ and $y\gt 0$}
\\\pi+\arctan(\frac yx)&\text{if $x\lt 0$}\end{cases}$$
Since we have
$$\arg(x+(y-1)i)=\begin{cases}
2\pi+\arctan(\frac{y-1}{x})&\text{if $x\gt 0$ and $y\lt 1$}
\\\arctan(\frac{y-1}x)&\text{if $x\gt 0$ and $y\geqslant 1$}
\\\frac{3}{2}\pi&\text{if $x=0$ and $y\lt 1$}
\\\text{undefined}&\text{if $x=0$ and $y=1$}
\\\frac{\pi}{2}&\text{if $x=0$ and $y\gt 1$}
\\\pi+\arctan(\frac{y-1}x)&\text{if $x\lt 0$}
\end{cases}$$
and
$$\arg(x+(y+1)i)=\begin{cases}
2\pi+\arctan(\frac{y+1}{x})&\text{if $x\gt 0$ and $y\lt -1$}
\\\arctan(\frac{y+1}x)&\text{if $x\gt 0$ and $y\geqslant -1$}
\\\frac{3}{2}\pi&\text{if $x=0$ and $y\lt -1$}
\\\text{undefined}&\text{if $x=0$ and $y=-1$}
\\\frac{\pi}{2}&\text{if $x=0$ and $y\gt -1$}
\\\pi+\arctan(\frac{y+1}x)&\text{if $x\lt 0$}
\end{cases}$$
we get
$$\arg(x+(y-1)i)-\arg(x+(y+1)i)$$
$$=\begin{cases}
2\pi+\arctan(\frac{y-1}{x})-(2\pi+\arctan(\frac{y+1}{x}))&\text{if $x\gt 0$ and $y\lt -1$}
\\2\pi+\arctan(\frac{y-1}{x})-\arctan(\frac{y+1}x)&\text{if $x\gt 0$ and $-1\leqslant y\lt 1$}
\\\arctan(\frac{y-1}x)-\arctan(\frac{y+1}x)&\text{if $x\gt 0$ and $y\geqslant 1$}
\\\frac{3}{2}\pi-\frac{3}{2}\pi&\text{if $x=0$ and $y\lt -1$}
\\\text{undefined}&\text{if $x=0$ and $y=-1$}
\\\frac{3}{2}\pi-\frac{\pi}{2}&\text{if $x=0$ and $-1\lt y\lt 1$}
\\\text{undefined}&\text{if $x=0$ and $y=1$}
\\\frac{\pi}{2}-\frac{\pi}{2}&\text{if $x=0$ and $y\gt 1$}
\\\pi+\arctan(\frac{y-1}x)-(\pi+\arctan(\frac{y+1}x))&\text{if $x\lt 0$}
\end{cases}$$
$$=\begin{cases}
\arctan(\frac{y-1}{x})-\arctan(\frac{y+1}{x})\lt 0&\text{if $x\gt 0$ and $y\lt -1$}
\\2\pi+\arctan(\frac{y-1}{x})-\arctan(\frac{y+1}x)\gt 2\pi&\text{if $x\gt 0$ and $-1\leqslant y\lt 1$}
\\\arctan(\frac{y-1}x)-\arctan(\frac{y+1}x)\lt 0&\text{if $x\gt 0$ and $y\geqslant 1$}
\\0&\text{if $x=0$ and $y\lt -1$}
\\\text{undefined}&\text{if $x=0$ and $y=-1$}
\\\pi&\text{if $x=0$ and $-1\lt y\lt 1$}
\\\text{undefined}&\text{if $x=0$ and $y=1$}
\\ 0&\text{if $x=0$ and $y\gt 1$}
\\\arctan(\frac{y-1}x)-\arctan(\frac{y+1}x)&\text{if $x\lt 0$}
\end{cases}$$
So, under the condition $x\lt 0$, we have
$$\arctan\bigg(\frac{y-1}x\bigg)-\arctan\bigg(\frac{y+1}x\bigg)= \frac{2\pi}{3}$$
i.e.
$$\arctan\left(\frac{2x}{1-x^2-y^2}\right)=-\frac{\pi}{3},$$
i.e.
$$\frac{2x}{1-x^2-y^2}=-\sqrt 3,$$
i.e.
$$\left(x-\frac{1}{\sqrt 3}\right)^2+y^2=\left(\frac{2}{\sqrt 3}\right)^2\tag1$$
Since the region we seek is the inside of the circle $(1)$ with $x\lt 0$, the area is given by
$$\pi\bigg(\frac{2}{\sqrt 3}\bigg)^2\times\frac{\frac{2}{3}\pi}{2\pi}-\frac 12\bigg(\frac{2}{\sqrt 3}\bigg)^2\sin\bigg(\frac{2\pi}{3}\bigg)=\color{red}{\frac{4}{9}\pi-\frac{1}{\sqrt 3}}$$
In the following, let us prove that if the principal value of the argument is chosen to be the unique value of the argument that lies within the interval $(−\pi,\pi]$, then, for any $z$ for which $\arg(z\pm i)$ are defined, $\arg(z-i)-\arg(z+i)\lt\frac{\pi}{2}$ holds.
Proof :
Let $z=x+yi$ where $x,y\in\mathbb R$.
If the principal value of the argument is chosen to be the unique value of the argument that lies within the interval $(−\pi,\pi]$, then we have
$$\arg(x+yi)=\begin{cases}\text{arctan}(\frac yx)&\text{if $x\gt 0$ and $y\geqslant 0$}
\\-\arctan(\frac{-y}{x})&\text{if $x\gt 0$ and $y\lt 0$}
\\\frac{\pi}{2}&\text{if $x=0$ and $y\gt 0$}
\\\text{undefined}&\text{if $x=0$ and $y=0$}
\\-\frac{\pi}{2}&\text{if $x=0$ and $y\lt 0$}
\\\pi-\arctan(\frac{y}{-x})&\text{if $x\lt 0$ and $y\geqslant 0$}
\\-(\pi-\arctan(\frac{-y}{-x}))&\text{if $x\lt 0$ and $y\lt 0$}\end{cases}$$
i.e.
$$\arg(x+yi)=\begin{cases}\text{arctan}(\frac yx)&\text{if $x\gt 0$}
\\\frac{\pi}{2}&\text{if $x=0$ and $y\gt 0$}
\\\text{undefined}&\text{if $x=0$ and $y=0$}
\\-\frac{\pi}{2}&\text{if $x=0$ and $y\lt 0$}
\\\arctan(\frac{y}{x})+\pi&\text{if $x\lt 0$ and $y\geqslant 0$}
\\\arctan(\frac yx)-\pi&\text{if $x\lt 0$ and $y\lt 0$}
\end{cases}$$
Since we have
$$\arg(x+(y-1)i)=\begin{cases}\text{arctan}(\frac{y-1}x)&\text{if $x\gt 0$}
\\\frac{\pi}{2}&\text{if $x=0$ and $1\lt y$}
\\\text{undefined}&\text{if $x=0$ and $y=1$}
\\-\frac{\pi}{2}&\text{if $x=0$ and $y\lt 1$}
\\\arctan(\frac{y-1}{x})+\pi&\text{if $x\lt 0$ and $1\leqslant y$}
\\\arctan(\frac{y-1}x)-\pi&\text{if $x\lt 0$ and $y\lt 1$}
\end{cases}$$
and
$$\arg(x+(y+1)i)=\begin{cases}\text{arctan}(\frac{y+1}x)&\text{if $x\gt 0$}
\\\frac{\pi}{2}&\text{if $x=0$ and $-1\lt y$}
\\\text{undefined}&\text{if $x=0$ and $y=-1$}
\\-\frac{\pi}{2}&\text{if $x=0$ and $y\lt -1$}
\\\arctan(\frac{y+1}{x})+\pi&\text{if $x\lt 0$ and $-1\leqslant y$}
\\\arctan(\frac{y+1}x)-\pi&\text{if $x\lt 0$ and $y\lt -1$}
\end{cases}$$
we get
$$\arg(x+(y-1)i)-\arg(x+(y+1)i)$$
$$=\begin{cases}\text{arctan}(\frac{y-1}x)-\text{arctan}(\frac{y+1}x)&\text{if $x\gt 0$}
\\-\frac{\pi}{2}-(-\frac{\pi}{2})&\text{if $x=0$ and $y\lt -1$}
\\\text{undefined}&\text{if $x=0$ and $y=-1$}
\\-\frac{\pi}{2}-\frac{\pi}{2}&\text{if $x=0$ and $-1\lt y\lt 1$}
\\\text{undefined}&\text{if $x=0$ and $y=1$}
\\\frac{\pi}{2}-\frac{\pi}{2}&\text{if $x=0$ and $1\lt y$}
\\\arctan(\frac{y-1}x)-\pi-(\arctan(\frac{y+1}x)-\pi)&\text{if $x\lt 0$ and $y\lt -1$}
\\\arctan(\frac{y-1}x)-\pi-(\arctan(\frac{y+1}{x})+\pi)&\text{if $x\lt 0$ and $-1\leqslant y\lt 1$}
\\\arctan(\frac{y-1}{x})+\pi-(\arctan(\frac{y+1}{x})+\pi)&\text{if $x\lt 0$ and $1\leqslant y$}\end{cases}$$
$$=\begin{cases}\text{arctan}(\frac{y-1}x)-\text{arctan}(\frac{y+1}x)\lt 0&\text{if $x\gt 0$}
\\0&\text{if $x=0$ and $y\lt -1$}
\\\text{undefined}&\text{if $x=0$ and $y=-1$}
\\-\pi&\text{if $x=0$ and $-1\lt y\lt 1$}
\\\text{undefined}&\text{if $x=0$ and $y=1$}
\\0&\text{if $x=0$ and $1\lt y$}
\\\arctan(\frac{y-1}x)-\arctan(\frac{y+1}x)\lt\frac{\pi}{2}&\text{if $x\lt 0$ and $y\lt -1$}
\\-2\pi+\arctan(\frac{y-1}x)-\arctan(\frac{y+1}{x})\lt 0&\text{if $x\lt 0$ and $-1\leqslant y\lt 1$}
\\\arctan(\frac{y-1}{x})-\arctan(\frac{y+1}{x})\lt\frac{\pi}{2}&\text{if $x\lt 0$ and $1\leqslant y$}\end{cases}$$
Therefore, we can say that, for any $z$ for which $\arg(z\pm i)$ are defined, $\arg(z-i)-\arg(z+i)\lt\frac{\pi}{2}$ holds.$\quad\blacksquare$