Her first row of discard shows a classic mentanpin hand (concealed, tanyao, pinfu). From this we can suppose she have a ryanmen wait and don't wait for an honor. Ones and Nines are more or less safe but can be tricky (_23_ is a good wait). If you need more explanations, please ask.
Knowing which

comes from the hand and which are draw-discarded is an interesting information and may change the reading.
I suppose the second

and the

are draw-discarded.
You should focus on

(it's the first "middle-tile" discard). Normally any tile between 3-7 is useful, why did she not need it?
You said the dora was 5 pin, so this 4 pin should be even more useful. She would never discard it without a very good reason (assuming she is not a total beginner).
Knowing if

comes from the hand or not is a very valuable info. The interpretation of the

would be completely different.
Same thing for the first

, why he don't need it?
I suppose

and at the second

are draw-discarded. If it's the case, they are meaningless. If not, she may be not going for mentanpin, or maybe there is a "special" table situation (see other players' discards).
"what the opponents are waiting for"
You have to sort out which tiles are discarded for being useless in his hand (like 9 from 129), and which ones was useful but he find a better one (like

from 223, 245, ...).
(I'm not sure this sentence is in valid English.)
Generally, useless tiles are discarded first and the more useful ones are discarded at the very end.
The last tile discarded from the hand, I suppose the

here, is likely to be very close to the waiting pattern (ex: 344, 445). But it can be otherwise too (ex: 4567).
In fact, it's easier to find what the opponents are NOT waiting for.
He is not waiting for a tile he had discarded (furiten).
Assuming he will have a ryanmen wait, if he is not waiting for a 4, he is probably not waiting for a 1 and 7. Same with 5 and 2/8, and with 6 and 3/9.
Beware! If he is not waiting for a 1, you should NOT consider 4 to be safe. He can have 56 and wait for 4-7.
"how to decide to break my hand"
Are you waiting?
How much worth your hand?
How much seems to worth your opponents hands?
Did you have save tiles?
...
For the given situation, South hand seems to worth 4-5 han (I let you count

) and it's pretty much late in the game.
If you are not tenpai, you should break your hand.
If your hand worth more than a mangan and don't have any safe tile, you will continue your hand.
There is more to say, but I will stay here for tonight.
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Edit1: Oh! If my reading is right, I'm not quite sure why he riichi: it's late in the game and a 3-4 han hand is already good.
Maybe it really improves his hand value (3->4 han), or maybe he hope for ura-dora (5 han + ??? dora).
Maybe the exact situation can explain it (opponent's discards, score, rank, ...).
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Edit2: "she ended up paying me for riichi pinfu haitei (I had riichi'd with pinfu only one turn earlier)"
Hum?! That doesn't sound right!
1) You are West, riichi.
2) North plays.
3) East plays.
4) South plays, riichi.
5) You win by drawing the last tile of the wall (haitei).
Normally, it's not allowed to riichi if less that 4 tiles remain in the wall, so South make a fault.
Let's assume Saki rules allow that, their is no point in South's riichi: he bet 1000 points and his only way to win is calling the last tile (houtei).
Second problem: it's the 14th discard. If we are one tile before the end, it should be the 18th discard or so.