Consegui uma emissão com sucesso depois desse ajuste:
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<email>
cli...@campinas.com</email>
</toma>
<serv>
<locPrest>
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</locPrest>
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<xDescServ>Serviço de Programação</xDescServ>
<cNBS>102010000</cNBS>
</cServ>
</serv>
<valores>
<vServPrest>
<vServ>1000.00</vServ>
</vServPrest>
<trib>
<tribMun>
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<tribFed>
<piscofins>
<CST>01</CST>
<vBCPisCofins>1000.00</vBCPisCofins>
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</piscofins>
</tribFed>
<totTrib>
<vTotTrib>
<vTotTribFed>0.00</vTotTribFed>
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</vTotTrib>
</totTrib>
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<indFinal>0</indFinal>
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<indDest>0</indDest>
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<trib>
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<cClassTrib>000001</cClassTrib>
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</valores>
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<Signature xmlns="
http://www.w3.org/2000/09/xmldsig#">
...
</Signature>
</DPS>