"We lost a hero this evening," Mayor Bill de Blasio said at a news conference outside Jacobi Medical Center.
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Mulkeen had served nearly seven years with the department and was a member of the Bronx Borough Anti-Crime Unit in the 47th Precinct. He lived in Yorktown Heights with his girlfriend, an NYPD police officer in the Bronx's 44th precinct.
Police say he had a promising future and 270 career arrests, the majority of which were felony arrests and many of which involved removing illegal guns from Bronx streets.
The track and field program at Fordham University in the Bronx posted that Mulkeen was an alumnus, a two-year field captain who competed from 2004-2008. He was a multiple-time scorer at the Atlantic 10 Championship in the weight throw for indoor track and the hammer throw for outdoor track, as well as a multiple-time IC4A Championship qualifier in the weight throw.
The university said he had recently decided to re-join his alma mater as a volunteer throwing coach, alongside his former teammate, head coach Brian Horowitz.
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Fordham flags will fly at half staff until after the officer's funeral.
"The Fordham family has lost one of its own to senseless violence today," Fordham president Joseph M. McShane, S.J., said. "Brian Mulkeen went out into the world to do exactly what we expect of our alumni, be a man for others, and he was slain in service to the local community. Our hearts go out to Brian's family and loved ones, and to his fellow officers. I know the Fordham community joins me in prayer for the repose of Brian's soul, and for his family and loved ones as they mourn his untimely death."
Mulkeen was also mourned in the town of Tuxedo, where he worked as a part-time dispatcher. He was a young man who graduated from two police academies, the first in Ulster County.
"He brought joy, and caring with him when he came," the Tuxedo Police Department posted on Facebook. "He followed his dream. He will always be one of us, remembered for his courage, his love and his drive. We will never forget, we will always be with you."
A somber 55-mile procession was held Monday morning as the NYPD transported the body of its fallen officer. Along the route were his brothers and sisters in blue, first responders and members of the public, all paying tribute, right down to his former school bus driver.
"These kids become part of your family," said Monroe resident Connie Angel. "And I treated him like one of my own children."
Mulkeen left a high-paying finance job to become a police officer because, as friend Daniel Tucker wrote on Facebook, he "felt like he wasn't doing enough with his life."
Mulkeen graduated from Fordham University's business school and worked as a financial adviser at Merrill Lynch in New York from 2007 to 2009, the company said.
In his Facebook post, Tucker recounted Mulkeen's departure from the company. He remembered his friend calling him and saying: "Tuck! I couldn't wait to tell you, I quit my job at Merrill Lynch and I'm gonna be a cop!"
Mayor de Blasio and NYPD officials met with Officer Mulkeen's family following the shooting.
"One of the things they told us, even with their grief, was that Brian made a choice, an incredibly noble choice to leave a civilian life, a lucrative career," de Blasio said. "He wanted to protect other people. He loves this city, he wanted to protect other people, and he put his life on the line, and he gave his life for all of us."
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New York Gov. Andrew Cuomo released a statement that read, in part:
"I am absolutely heartbroken by the tragic loss of NYPD Officer Brian Mulkeen, who was shot and killed in the line of duty early Sunday morning in The Bronx. At 33, Officer Mulkeen was taken far, far too early from his family and from the city he sacrificed everything to protect. He is the embodiment of bravery and a true New York hero."
A wake will be held Thursday from 1 p.m. to 4 p.m. and 6 p.m. to 9 p.m. at Smith, Seaman & Quackenbush Funeral Home, located at 117 Maple Avenue East in Monroe.
His funeral will be held Friday 11 a.m. at the Church of the Sacred Heart, located at 26 Still Road in Monroe.
(The Associated Press contributed to this report.)
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