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Grimaldi (19), a part-time quantity surveying student at Otago Polytechnic, qualified fifth-fastest for yesterday's final, but improved on the ranking by one spot in the final despite running 0.04sec slower than her heat time of 12.88sec, a personal-best.
Grimaldi started off on par with most of the field in the final, which was reduced to a field of seven halfway through the race when Cuban Yunidis Castillo pulled up with injury.
The New Zealander kept fighting to the line, dashing the 100m in 12.96, finishing 0.12sec behind Brazilian Teresinha De Jesus Correia Santos, who won bronze with a late burst in the outside lane.
American sprinter Deja Young won the final in 12.15sec with Alicja Fiodorow, of Poland, claiming silver in 12.46sec.
Less than half an hour later, star swimmer Sophie Pascoe won her second gold of the Games after defending her title in the 200m individual medley SM10 final
It was Pascoe's 13th medal in total third of her Rio campaign following a gold in the 100m backstroke S10 and silver medal in the 50m freestyle S10.
She broke her own world record to claim the 200m individual medley SM10 event for the third straight Olympics. The 23-year-old finished in a time of 2min 24.90sec, more than 5sec clear of Canadian Aurelie Rivard. Bianka Rap on Hungary took the bronze.
It was New Zealand's fourth gold of the Games and took the team's total tally to nine.
Emma Foy and Laura Thompson (sighted pilot) showed true guts and determination to win silver on the final day of racing at the Rio Velodrome at the Paralympics. The duo qualified for the gold medal ride in the women's B 3000m individual pursuit, finishing second behind the British tandem in 3min 31.569sec. - Additional reporting The New Zealand Herald