you might want to use format-number to avoid
<MassPercent>40.349999999999994</MassPercent>
but:
<xsl:stylesheet version="2.0"
xmlns:xsl="http://www.w3.org/1999/XSL/Transform">
<xsl:template match="*">
<xsl:copy>
<xsl:copy-of select="@*"/>
<xsl:apply-templates/>
</xsl:copy>
</xsl:template>
<xsl:template match="LeafExtName">
<xsl:variable name="m" select="max(*/*/MassPercent)"/>
<xsl:copy>
<xsl:copy-of select="@*"/>
<xsl:apply-templates >
<xsl:with-param name="mp"
select="(*/*/MassPercent[number(.)=$m])[1]" tunnel="yes"/>
<xsl:with-param name="t" select="sum(*/*/MassPercent)" tunnel="yes"/>
</xsl:apply-templates>
</xsl:copy>
</xsl:template>
<xsl:template match="MassPercent">
<xsl:param name="mp" tunnel="yes"/>
<xsl:param name="t" tunnel="yes"/>
<xsl:copy>
<xsl:value-of select="if(. is $mp) then . + 100 - $t else ."/>
</xsl:copy>
</xsl:template>
</xsl:stylesheet>
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