ALBERT

Description: Accurate pH measurements in polar waters and sea ice brines require pH indicator dyes characterized at near-zero and below-zero temperatures and high salinities. We present experimentally determined physical and chemical characteristics of purified meta-Cresol Purple (mCP) pH indicator dye suitable for pH measurements in seawater and conservative seawater-derived brines at salinities (S) between 35 and 100 and temperatures (T) between their freezing point and 298.15 K (25 °C). Within this temperature and salinity range, using purified mCP and a novel thermostated spectrophotometric device, the pH on the total scale (pHT) can be calculated from direct measurements of the absorbance ratio R of the dye in natural samples as pHT=−log(kT2e2)+log(R−e11−Re3e2) Based on the mCP characterization in these extended conditions, the temperature and salinity dependence of the molar absorptivity ratios and − log(kT2e2) of purified mCP is described by the following functions: e1 = −0.004363 + 3.598 × 10−5T, e3/e2 = −0.016224 + 2.42851 × 10−4T + 5.05663 × 10−5(S − 35), and − log(kT2e2) = −319.8369 + 0.688159 S −0.00018374 S2 + (10508.724 − 32.9599 S + 0.059082S2) T−1 + (55.54253 − 0.101639 S) ln T −0.08112151T. This work takes the characterisation of mCP beyond the currently available ranges of 278.15 K ≤ T ≤ 308.15 K and 20 ≤ S ≤ 40 in natural seawater, thereby allowing high quality pHT measurements in polar systems.

Description: Marine carbonate chemistry measurements have been carried out annually since 2009 during UK research cruises along the Extended Ellett Line (EEL), a hydrographic transect in the northeast Atlantic Ocean. The EEL intersects several water masses that are key to the global thermohaline circulation, and therefore the cruises sample a region in which it is critical to monitor secular physical and biogeochemical changes. We have combined results from these EEL cruises with existing quality-controlled observational data syntheses to produce a hydrographic time series for the EEL from 1981 to 2013. This reveals multidecadal increases in dissolved inorganic carbon (DIC) throughout the water column, with a near-surface maximum rate of 1.800.45 mu molkg(-1)yr(-1). Anthropogenic CO2 accumulation was assessed, using simultaneous changes in apparent oxygen utilization (AOU) and total alkalinity (TA) as proxies for the biogeochemical processes that influence DIC. The stable carbon isotope composition of DIC (C-13(DIC)) was also determined and used as an independent test of our method. We calculated a volume-integrated anthropogenic CO2 accumulation rate of 2.80.4mgCm(-3)yr(-1) along the EEL, which is about double the global mean. The anthropogenic CO2 component accounts for only 316% of the total DIC increase. The remainder is derived from increased organic matter remineralization, which we attribute to the lateral redistribution of water masses that accompanies subpolar gyre contraction. Output from a general circulation ecosystem model demonstrates that spatiotemporal heterogeneity in the observations has not significantly biased our multidecadal rate of change calculations and indicates that the EEL observations have been tracking distal changes in the surrounding North Atlantic and Nordic Seas.

Description: The uptake of anthropogenic CO2 by the oceans since the onset of the industrial revolution is considered a serious challenge to marine ecosystems due to ensuing carbonate-chemistry changes (ocean acidification). Furthermore, the CO2 uptake is reducing the ocean's capacity to absorb future CO2 emissions. In order to follow the changes in the ocean's carbonate system, high-quality analytical measurements with good spatial and temporal resolution are necessary. High-precision and accurate pH measurements are now possible, and allow us to determine the progression of ocean acidification. The spectrophotometric pH technique is now widely used and capable of the required high-quality measurements. Spectrophotometric pH systems are deployed on ships and in situ on remote platforms. Smaller and more rugged instruments are nevertheless required for more widespread in situ application to allow routine high-resolution measurements, even in the most remote regions. We critically review oceanic pH measurements, and focus on state-of-the-art spectrophotometric pH measurement techniques and instrumentation. We present a simple microfluidic design integrated in a shipboard instrument featuring high accuracy and precision as a key step towards a targeted pH microsensor system