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He was born in Edinburgh on 29 April 1817, the son of Thomas White, a banker's clerk, and his wife, Mary Ann Gellatly. He was baptized in Kirkurd, Peebles, on 2 August 1818 and was educated at the high school in Edinburgh. When he was eighteen he went to London with a letter of introduction to John Edward Gray of the British Museum and obtained employment in the zoological branch of the department of natural history in December 1835. To begin with his work was directed by the keeper, John George Children. On Children's retirement in 1840, supervision passed to Gray, his energetic successor. Once Gray had established a simple method for the systematic registration of specimens in the zoological department, he made preparations to publish catalogues of them. White was one of four assistants charged with carrying out these tasks. Some of his early work on the arthropod group was hindered by George Samouelle, a fellow assistant who had taken to drink and spited White by removing the registration numbers on many specimens. However, Samouelle was sacked in 1841 and, following the appointment of Edward Doubleday in 1842, White was able to concentrate uninterrupted on the Coleoptera and on Crustacea.
On 27 January 1844 he married Helen Bolden (b. 1808/9, d. in or before 1861), daughter of William Bolden, a bookbinder. The couple had one daughter.
At the museum, White produced a List of the Specimens of Crustacea in the Collection of the British Museum (1847), wrote most parts of Nomenclature of Coleopterous Insects in the Collection of the British Museum (9 parts, 1847?55), and contributed to the List of Specimens of British Animals in the Collection of the British Museum (1850?55). He also published a number of other books, including A Popular History of Mammalia (1850), A Popular History of Birds (1855), The Instructive Picture Book (with R. M. Stark, 1857), and Heads and Tails (1870). He contributed two works to the Society for Promoting Christian Knowledge's Diagrams of Natural History series (c.1860), and between 1839 and 1867 wrote more than sixty scientific papers. Although known for his work on arthropods, he was also a keen botanist and was the first to apply the suffix ?-idea? to designate the family names of insects.
White was elected a fellow of the Linnean Society in 1846. He was a member of the Entomological Society of London from 1839 to 1863, and a member of the Botanical Society of London. Visitors to the museum remembered White's readiness to assist and his scientific knowledge earned him their respect. Unfortunately, he was not always on such good terms with Gray, and never rose above the assistant grade. Nevertheless, employment at the British Museum provided him with first-hand knowledge of the advantages enjoyed by a national museum and, using the pseudonym Arachnophilus, he wrote to Scottish newspapers advocating the establishment of a national museum for Scotland. The letters were also published separately as Four Short Letters (n.d. [1850]).
White's wife, Helen, died in or before 1861, and grief caused him to have a nervous breakdown. He was for a time committed to an asylum in Scotland and retired from the museum on a small pension in 1863. On 28 July 1862 he married his second wife, Margaret Watson, daughter of Alexander Watson, farmer. The couple's first son was born in 1863; by 1874 they had at least two more. However, White's new-found happiness was marred by financial worries and he died intestate at 111 St Andrews Road, Pollokshields, on 30 December 1878.
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