Posts Tagged 'methods'

The analysis of dissolved inorganic carbon in liquid using a microfluidic conductivity sensor with membrane separation of CO2

Autonomous and continuous analysis of ocean chemistry, in particular dissolved inorganic carbon(DIC)concentration profiles with depth, are of great significance with regard to ocean acidification and climate change. However, the development of suitable miniature in-situ analysis systems is hampered by the size, cost and power requirements of traditional optical analysis instrumentation. Here we report a low-cost alternative approach based on CO2 separation and conductance measurement in microfluidic cells that could pave the way to integrated lab on chip systems for long-term ocean float deployment. Conductimetric determination of dissolved inorganic carbon concentration, in the seawater range of 1000 –3000 mol kg-1, has been achieved using a microfluidic thin film electrode conductivity cell and a membrane-based gas exchange cell. After transfer across the membrane, the eluted CO2 reacted in a NaOH carrier, was drawn through a conductivity cell with a <1L interelectrode volume, where the change in impedance versus time was measured. Precision values, obtained from relative standard deviation,were ~ 0.2% for peak height measurements over extended time periods. This compares favourably with precision values of ~ 0.25% obtained using a large C4D electrophoresis headstage with similar measurement volume. The required sample and reagent volumes amounted to ~500L in total due to the incorporation of a planar membrane into a small volume exchange cell. This compares very favourably with previous attempts at conductivity based DIC analysis where total volumes between 5000L and 10000L were required. The use of long membrane tubes and macroscopic wire electrodes is avoided by incorporating a planar membrane (PDMS) between sample and exchange cell and by sputter deposition of Ti/Au multilayer electrode patterns directly onto a patterned thermoplastic (PMMA) manifold. Future performance improvement will require addressing membrane chemical and mechanical stability as well as further volume reduction and component integration into a single manifold.

Continue reading ‘The analysis of dissolved inorganic carbon in liquid using a microfluidic conductivity sensor with membrane separation of CO2’

Calcite dissolution rates in seawater: lab vs. in-situ measurements and inhibition by organic matter


• Calcite dissolution in lab and in-situ exhibits the same dissolution mechanisms.

• In-situ dissolution rates are likely inhibited by dissolved organic carbon.

• Orthophosphate has no effect on seawater calcite dissolution rates from pH 5.5 to 7.5.

• Previous in-situ dissolution rates fall between bounds established by our measurements.

• Rate measurements suggest need to reevaluate marine carbonate system equilibria.


Ocean acidification from fossil fuel burning is lowering the mean global ocean saturation state (Ω = ), thus increasing the thermodynamic driving force for calcium carbonate minerals to dissolve. This dissolution process will eventually neutralize the input of anthropogenic CO2, but the relationship between Ω and calcite dissolution rates in seawater is still debated. Recent advances have also revealed that spectrophotometric measurements of seawater pHs, and therefore in-situ Ωs, are systematically lower than pHs/Ωs calculated from measurements of alkalinity (Alk) and total dissolved inorganic carbon (DIC). The calcite saturation horizon, defined as the depth in the water column where Ω = 1, therefore shifts by ~5–10% depending on the parameters used to calculate Ω. The “true” saturation horizon remains unknown. To resolve these issues, we developed a new in-situ reactor and measured dissolution rates of 13C-labeled inorganic calcite at four stations across a transect of the North Pacific Ocean. In-situ saturation was calculated using both Alk-DIC (Ω(Alk, DIC)) and Alk-pH (Ω(Alk, pH)) pairs. We compare in-situ dissolution rates with rates measured in filtered, poisoned, UV-treated seawater at 5 and 21 °C under laboratory conditions. We observe in-situ dissolution above Ω(Alk, DIC) = 1, but not above Ω(Alk, pH) = 1. We emphasize that marine carbonate system equilibria should be reevaluated and that care should be taken when using proxies calibrated to historical Ω(Alk, DIC). Our results further demonstrate that calcite dissolution rates are slower in-situ than in the lab by a factor of ~4, but that they each possess similar reaction orders (n) when fit to the empirical Rate = k(1-Ω)n equation. The reaction orders are n < 1 for 0.8 < Ω < 1 and n = 4.7 for 0 < Ω < 0.8, with the kink in rates at Ωcrit = 0.8 being consistent with a mechanistic transition from step edge retreat to homogenous etch pit formation. We reconcile the offset between lab and in-situ rates by dissolving calcite in the presence of elevated orthophosphate (20 μm) and dissolved organic carbon (DOC) concentrations, where DOC is in the form of oxalic acid (20 μm), gallic acid (20 μm), and d-glucose (100 μm). We find that soluble reactive phosphate has no effect on calcite dissolution rates from pH 5.5–7.5, but the addition of DOC in the form of d-glucose and oxalic acid slows laboratory dissolution rates to match in-situ observations, potentially by inhibiting the retreat rate of steps on the calcite surface. Our lab and in-situ rate data form an envelope around previous in-situ dissolution measurements and may be considered outer bounds for dissolution rates in low/high DOC waters. The lower bound (high DOC) is most realistic for particles formed in, and sinking out of, surface waters, and is described by R(mol cm-2 s-1) = 10–14.3±0.2(1-Ω)0.11±0.1 for 0.8 < Ω < 1, and R(mol cm-2 s-1) = 10–10.8±0.4(1-Ω)4.7±0.7 for 0 < Ω < 0.8. These rate equations are derived from in-situ measurements and may be readily implemented into marine geochemical models to describe water column calcite dissolution.

Continue reading ‘Calcite dissolution rates in seawater: lab vs. in-situ measurements and inhibition by organic matter’

Impact of ocean acidification on crystallographic vital effect of the coral skeleton

Distinguishing between environmental and species-specific physiological signals, recorded in coral skeletons, is one of the fundamental challenges in their reliable use as (paleo)climate proxies. To date, characteristic biological bias in skeleton-recorded environmental signatures (vital effect) was shown in shifts in geochemical signatures. Herein, for the first time, we have assessed crystallographic parameters of bio-aragonite to study the response of the reef-building coral Stylophora pistillata to experimental seawater acidification (pH 8.2, 7.6 and 7.3). Skeletons formed under high pCO2 conditions show systematic crystallographic changes such as better constrained crystal orientation and anisotropic distortions of bio-aragonite lattice parameters due to increased amount of intracrystalline organic matrix and water content. These variations in crystallographic features that seem to reflect physiological adjustments of biomineralizing organisms to environmental change, are herein called crystallographic vital effect (CVE). CVE may register those changes in the biomineralization process that may not yet be perceived at the macromorphological skeletal level.

Continue reading ‘Impact of ocean acidification on crystallographic vital effect of the coral skeleton’

An enhanced ocean acidification observing network: from people to technology to data synthesis and information exchange

A successful integrated ocean acidification (OA) observing network must include (1) scientists and technicians from a range of disciplines from physics to chemistry to biology to technology development; (2) government, private, and intergovernmental support; (3) regional cohorts working together on regionally specific issues; (4) publicly accessible data from the open ocean to coastal to estuarine systems; (5) close integration with other networks focusing on related measurements or issues including the social and economic consequences of OA; and (6) observation-based informational products useful for decision making such as management of fisheries and aquaculture. The Global Ocean Acidification Observing Network (GOA-ON), a key player in this vision, seeks to expand and enhance geographic extent and availability of coastal and open ocean observing data to ultimately inform adaptive measures and policy action, especially in support of the United Nations 2030 Agenda for Sustainable Development. GOA-ON works to empower and support regional collaborative networks such as the Latin American Ocean Acidification Network, supports new scientists entering the field with training, mentorship, and equipment, refines approaches for tracking biological impacts, and stimulates development of lower-cost methodology and technologies allowing for wider participation of scientists. GOA-ON seeks to collaborate with and complement work done by other observing networks such as those focused on carbon flux into the ocean, tracking of carbon and oxygen in the ocean, observing biological diversity, and determining short- and long-term variability in these and other ocean parameters through space and time.

Continue reading ‘An enhanced ocean acidification observing network: from people to technology to data synthesis and information exchange’

Spectrophotometric determination of pH and carbonate ion concentrations in seawater: choices, constraints and consequences

• Spectrophotometric pH and carbonate ion measurements in seawater.

• Different application platforms, such as shipboard, underway, in situ, etc.

• Quality improvement with indicator purification, sample pre-treatment, etc.

• Carbonate ion to be considered as the fifth parameter describing carbonate system.

Accurate and precise marine CO2 system measurements are important for marine carbon cycle research and investigations of ocean acidification. Seawater pH is important because it can be used to characterize a wide range of chemical and biogeochemical processes. Saturation states of calcium carbonate minerals, which are directly proportional to carbonate ion concentration ([CO32-]), influence biogenic calcification and rates of carbonate dissolution. Spectrophotometric pH and carbonate ion measurements can both benefit greatly from the high sensitivity, stability, consistency and processing speed made possible through automation. Spectrophotometric methods are well-suited for shipboard, underway and in situ deployments under harsh conditions. Spectrophotometric pH measurements typically have a reproducibility of 0.0004-0.001 for shipboard and laboratory measurements and 0.0014-0.004 for in situ measurements. Shipboard spectrophotometric measurements of [CO32-] are becoming common on research expeditions. This review highlights the development of methods and instrumentation for spectrophotometric pH and [CO32-] measurements, and discusses the pros and cons of current technology. A comprehensive summary of the analytical merits of different flow analysis instruments is given. Aspects of measurement protocols that bear on the quality of pH and [CO32-] measurements, such as indicator purification, sample pretreatment, etc., are also described. Based on three decades of experience with seawater analysis, this review includes method recommendations and perspectives directly applicable or potentially applicable to pH and [CO32-] analysis of seawater.

Continue reading ‘Spectrophotometric determination of pH and carbonate ion concentrations in seawater: choices, constraints and consequences’

In vivo 31P-MRS of muscle bioenergetics in marine invertebrates: future ocean limits scallops’ performance


Dynamic in vivo 31P-NMR spectroscopy in combination with Magnetic Resonance Imaging (MRI) was used to study muscle bioenergetics of boreal and Arctic scallops (Pecten maximus and Chlamys islandica) to test the hypothesis that future Ocean Warming and Acidification (OWA) will impair the performance of marine invertebrates.

Materials & methods

Experiments were conducted following the recommendations for studies of muscle bioenergetics in vertebrates. Animals were long-term incubated under different environmental conditions: controls at 0 °C for C. islandica and 15 °C for P. maximus under ambient PCO2 of 0.039 kPa, a warm exposure with +5 °C (5 °C and 20 °C, respectively) under ambient PCO2 (OW group), and a combined exposure to warmed acidified conditions (5 °C and 20 °C, 0.112 kPa PCO2, OWA group). Scallops were placed in a 4.7 T MR animal scanner and the energetic status of the adductor muscle was determined under resting conditions using in vivo 31P-NMR spectroscopy. The surplus oxidative flux (Qmax) was quantified by recording the recovery of arginine phosphate (PLA) directly after moderate swimming exercise of the scallops.


Measurements led to reproducible results within each experimental group. Under projected future conditions resting PLA levels (PLArest) were reduced, indicating reduced energy reserves in warming exposed scallops per se. In comparison to vertebrate muscle tissue surplus Qmax of scallop muscle was about one order of magnitude lower. This can be explained by lower mitochondrial contents and capacities in invertebrate than vertebrate muscle tissue. Warm exposed scallops showed a slower recovery rate of PLA levels (kPLA) and a reduced surplus Qmax. Elevated PCO2 did not affected PLA recovery further.


Dynamic in vivo 31P-NMR spectroscopy revealed constrained residual aerobic power budgets in boreal and Arctic scallops under projected ocean warming and acidification indicating that scallops are susceptible to future climate change. The observed reduction in muscular PLArest of scallops coping with a warmer and acidified ocean may be linked to an enhanced energy demand and reduced oxygen partial pressures (PO2) in their body fluids. Delayed recovery from moderate swimming at elevated temperature is a result of reduced PLArest concentrations associated with a warm-induced reduction of a residual aerobic power budget.
Continue reading ‘In vivo 31P-MRS of muscle bioenergetics in marine invertebrates: future ocean limits scallops’ performance’

A new software of calculating the pH values of coastal seawater: considering the effects of low molecular weight organic acids


• Low molecular weight organic acids concentrations were high in the coastal seawater.

• Low molecular weight organic acids can reduce the pH value of the seawater.

• Software of Org·TCO2TA can more accurately calculate the pH of the coastal seawater.


Effects of low molecular weight organic acids (LMWOAs) on the pH value of seawater were investigated in the surface seawater of the Jiaozhou Bay, China. The new software of Org·TCO2TA was developed to calculate the pH values of seawater based on the alkalinity (Alk) equation where organic acid Alk (Org-Alk) was separated into LMWOA Alk (LMWOA-Alk) and humic acid Alk (HA-Alk). In the calculations, all dissociation constants of organic acids were from previous literature. In our study, the average concentration of total LMWOAs was 14.5 ± 11.2 μmol·kg−1 SW. pH values from the Org·TCO2TA software were closer to the pH values from spectrophotometric measurement than those from the CO2SYS program, indicating pH values can be influenced by high concentrations of LMWOAs in coastal seawater of the Jiaozhou Bay. Although the differences still existed between the pH values from the spectrophotometric method and the calculated pH values from the Org·TCO2TA software due to the influence of various factors, including the analytical errors of dissolved inorganic carbon and nutrients, the new software can calculate the pH values of coastal seawater more accurately by considering the effects of LMWOAs.

Continue reading ‘A new software of calculating the pH values of coastal seawater: considering the effects of low molecular weight organic acids’

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Ocean acidification in the IPCC AR5 WG II

OUP book