Pick up the bitten sibling, comfort her, make sure the wound is seen too, then distract with something while you talk to the one who did the biting: "I know you are feeling frustrated right now because I can't do what you want with you or you need help and I'm busy. It is hard to wait for something you want, I feel like that too sometimes. Biting your sister doesn't help though. Everyone gets upset when someone is bitten. It's important to say sorry to your sister for hurting her."
Maybe focus on positive reinforcement when he does it: "Gentle with other people, gentle touch."
Keep up a constant chatter to both children while you are doing other things. If he is feeling insecure (and thus the need for attention which drives the biting behaviour) talking to him (both children) will remind him that you know he is there, that you love him, are paying (some kind of) attention to him and what is interesting him.
Offer him something that has the same kind of give as skin/body to bite such as a 'chewy tube' when he does it: "If you feel like biting, have a go on this, as biting hurts people." Children of this age learn through their senses. They are more acutely aware of them than we are as adults. It may feel pleasant to bite, something we usually only associate with food. However, adults also bite their fingernails when anxious or bored.
Does he understand that biting causes his sister pain? How would you gauge his empathy? It is not uncommon for children to take until age six to develop empathy. If you think he has the ability to understand, ask him to remember a time when he got hurt (easier to remember than when he was bitten, if he has been) and say that biting hurts. I used to do that with my kids: I would help them to remember how it felt to be in the same situation but as the copping the pain. Sometimes I'd have to lead them into the memory; just thinking about it wasn't enough, remembering the emotion, how it felt, worked better. This may be more useful for older children.
Remind him often that he can come to you and ask you before you get busy, or before he gets angry or frustrated, perhaps helping him recognise the signs that show that he is getting angry - feeling tense in the stomach, for example.
Jot down a note about what's going on when it happens and see if you can see a pattern...
Be assertive about 'no biting'. If you can don't react angrily. It's not easy, especially when one child is screaming in pain and the other child is ignoring the resultant chaos.
Encourage gentle play and touch with toys, notice and comment when he's playing gentle, more than when he's playing rough. I think we parents all fall into the trap of noticing and commenting more when our children do annoying things and take advantage of when they are being quite and 'good' to get on with the chores, have some time to ourselves, etc.
Further reading:
- Biting in the Toddler Years
http://www.naturalchild.org/guest/linda_passmark.html - Natural Parenting When Toddlers Bite
http://www.naturalparenting.com.au/blog/article/when-toddlers-bite/ - Gentle Discipline for Toddlers: Biting, Hitting and Impulse Control
http://www.theparentvortex.com/wordpress/gentle-discipline-for-toddlers-biting-hitting-and-impulse-control/ - Aha! Parenting Toddler Biting
http://www.ahaparenting.com/ask-the-doctor-1/toddler-biting - Ask Dr Sears Biting and Hitting 18 Ways to Stop It
http://www.askdrsears.com/topics/discipline-behavior/bothersome-behaviors/biting-and-hitting-16-ways-stop-it
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