Возможность:
import org.apache.spark.sql.expressions._
import org.apache.spark.sql.functions._
val df = sc.parallelize(Seq(
("A", "X", 2, 100), ("A", "X", 7, 100), ("B", "X", 10, 100),
("C", "X", 1, 100), ("D", "X", 50, 100), ("E", "X", 30, 100)
)).toDF("c1", "c2", "Val1", "Val2")
val df2 = df
.groupBy("c1")
.agg(sum("Val1").alias("sum"))
.withColumn("fraction", col("sum") / sum("sum").over())
df2.show