<esri:FeatureLayer ID="AllAvailableFeatureLayer" Url="http://gismaps.pagnet.org/ArcGIS/rest/services/testprojectALLBikeCounts/MapServer/0" MouseLeftButtonUp="AllAvailableFeatureLayer_MouseLeftButtonUp" SelectionColor="Yellow" OutFields="*" Where="VolunteerAM='Available' and VolunteerPM<>'Available'" />
datetime <= '2011/09/13 08:53:38 UTC'
At first glance, your code looks good except if your field is a coded domain. In this case you have to use the code value for 'Available'.
Where="VolunteerAM = 'Available' and VolunteerPM != 'Available'"
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