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Metz
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A closer option, 2km walk from the center, is to walk along Boulevard du Pontiffroy towards northwest. Turn right on the Rue Ardant du Picq (Follow the signs saying Luxembourg/Thionville). After crossing two bridges comes the ramp to the highway. I hitched right before the ramp, on the bridge. See the map. Might be a bit problematic during rush-hour, then it could be better to hitch with a sign right after the roundabout on the end of Boulevard du Pontiffroy.
===Going South (France, Spain, etc.)===
I got a lift off a truck driver at an industrial zone roundabout just before the A31/E23 motorway, South West of Metz (less than 10 KM from city centre). It took me 60 minutes to get a ride at the Z.A.C d'augney area. This can be reached by the number 101 bus from Metz City Centre for around 1.50 Euro