Nutrients and oxygen concentrations measured in water samples from the North Atlantic during the James Cook cruise JC087 in March 2013

Analysis for micro-molar concentrations of nitrate and nitrite, nitrite, phosphate, silicate and ammonia was undertaken on a SEAL Analytical UK Ltd, AA3 segmented flow autoanalyser following methods described by Kirkwood (1996). Samples were drawn from Niskin bottles on the CTD into 15ml polycarbonate centrifuge tubes and kept refrigerated at approximately 4oC until analysis, which generally commenced within 30 minutes. Overall 23 runs with 597 samples were analysed. This is a total of 502 CTD samples, 69 underway samples and 26 from other sources. An artificial seawater matrix (ASW) of 40g/litre sodium chloride was used as the inter-sample wash and standard matrix. The nutrient free status of this solution was checked by running Ocean Scientific International (OSI) low nutrient seawater (LNS) on every run. A single set of mixed standards were made up by diluting 5mM solutions made from weighed dried salts in 1litre of ASW into plastic 250ml volumetric flasks that had been cleaned by washing in MilliQ water (MQ). Data processing was undertaken using SEAL Analytical UK Ltd proprietary software (AACE 6.07) and was performed within a few hours of the run being finished. The sample time was 60 seconds and the wash time was 30 seconds. The lines were washed daily with wash solutions specific for each chemistry, but comprised of MQ, MQ and SDS, MQ and Triton-X, or MQ and Brij-35. Three times during the cruise the phosphate and silicate channels were washed with a weak sodium hypochlorite solution.

Stratigraphic first occurrence of Emiliania huxleyi in sediments of the Chatham Rise (Table 2)

A quantitative analysis was carried out of planktonic diatoms (biogenic opal) and calcareous nannofossils (biogenic calcite) in late Quaternary sediments (MIS 1-6) from four cores along a N-S transect east of New Zealand from 39°50'S to 50°04'S across the E-W-trending submarine ridge, the Chatham Rise. This was done to trace movements of oceanic fronts and to improve calcareous nannofossil stratigraphy for the last 130 000 yr in the SW Pacific. Sites ODP 1123 and Q 858 are below present day subtropical surface waters north of Chatham Rise. Site DSDP 594 is below present-day mixed temperate-subantarctic surface water south of the rise, and site ODP 1120 is below subantarctic surface water. The more diverse and opportunistic planktonic diatoms provided marker species for subtropical surface waters (Alveus marina, Fragilariopsis doliolus, Rhizosolenia bergonii and Azpeitia nodulifer) and others for subantarctic surface waters (Nitzschia kerguelensis, Thalassiosira lentiginosa). Application of these tracers permits the following conclusions: (1) subtropical conditions persisted north of Chatham Rise throughout the past 130 000 yr, in spite of the cooling of surface waters during colder periods; (2) during warm times (MIS 5 and MIS 3, and in MIS 1), the sporadic occurrence of subtropical species south of Chatham Rise indicates occasional admixture of subtropical surface waters that far south; (3) subantarctic waters extended to the southern slopes of the Chatham Rise during MIS 5b, late MIS 5a to early MIS 4, during the warmer time intervals in early MIS 3, and during latest MIS 3 to early MIS 2; (4) subantarctic frontal conditions existed over southern Chatham Rise during early MIS 4 and late MIS 3 to early MIS 2; and (5) it is probable that during cooler times, MIS 6, MIS 5b, and in MIS 2, intensified particle transport from the Bounty Trough to the northern flank of Chatham Rise occurred by intensified boundary currents. The larger abundance fluctuations in both microfossil groups at the sites south of Chatham Rise than north of Chatham Rise reflect northward shifts of the Circumpolar Subantarctic Water (CSW) and a contemporaneous disappearance of Australasian Subantarctic Water (ASW), implying an elevated temperature gradient between the surface water masses north and south of the Chatham Rise at the times of such northward shifts of CSW. Calcareous nannofossils are less diverse than diatoms, and are less specialised. Some calcareous nannofossil species show abundance shifts at the same time at different latitudes. Two of these abundance shifts can be used for correlation between subtropical and subantarctic sediments in the SW Pacific: (1) reversal in the relative abundance of Calcidiscus leptoporus and Coccolithus pelagicus associated with the MIS 2/1 boundary; and (2) drop in abundance of Gephyrocapsa muellerae or medium-sized Gephyrocapsa at the MIS 4/3 boundary. An additional abundance shift seems to be restricted to subtropical to mixed temperate-subtropical-subantarctic surface waters: (3) increase in abundance of G. muellerae or medium-sized Gephyrocapsa at the beginning of MIS 2 below the Okareka tephra.