A hybrid conductometric/spectrophotometric method for determining ionic strength of dilute aqueous solutions.

This work describes a novel conductometric/spectrophotometric method to determine the ionic strength (I) of dilute aqueous solutions (e.g., natural waters from rivers and lakes).

Reef Metabolism Monitoring Methods and Potential Applications for Coral Restoration.

Coral reef metabolism measurements have been used by scientists for decades to track reef responses to the globe's changing carbon budget and project shifts in reef function. Here, we propose that metabolism measurement tools and methods could also be used to monitor reef ecosystem change in response to coral restoration. This review paper provides a general introduction to net ecosystem metabolism and carbon chemistry for coral reef ecosystems, followed by a review of five metabolism monitoring methods with potential for application to coral reef restoration monitoring.

Purification and Physical-Chemical Characterization of Bromocresol Purple for Carbon System Measurements in Freshwaters, Estuaries, and Oceans.

This work provides an algorithm to describe the salinity ( ) and temperature () dependence of the equilibrium and molar absorptivity characteristics of purified bromocresol purple (BCP, a pH indicator) over a river-to-sea range of salinity (0 ≤ ≤ 40). Based on the data obtained in this study, the pH of water samples can be calculated on the seawater pH scale as follows: pH = -log( ) + log(( - )/(1 - )) where -log( ) = 4.981 - 0.

Purification and characterization of thymol blue for spectrophotometric pH measurements in rivers, estuaries, and oceans.

Thymol blue (TB) is one of a suite of indicator dyes appropriate for spectrophotometric determinations of the pH of aqueous solutions. For measurements of seawater pH, meta-cresol purple (mCP) is most often used, but TB is especially well suited for measurements in surface or shallow waters where the pH may exceed the optimal indicating range of mCP (e.g.

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

Accurate and precise marine CO 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 ([CO]), influence biogenic calcification and rates of carbonate dissolution.

Avoiding timescale bias in assessments of coastal wetland vertical change.

There is concern that accelerating sea-level rise will exceed the vertical growth capacity of coastal-wetland substrates in many regions by the end of this century. Vertical vulnerability estimates rely on measurements of accretion and/or surface-elevation-change derived from soil cores and/or surface elevation tables (SETs). To date there has not been a broad examination of whether the multiple timescales represented by the processes of accretion and elevation change are equally well-suited for quantifying the trajectories of wetland vertical change in coming decades and centuries.

Spectrophotometric calibration procedures to enable calibration-free measurements of seawater calcium carbonate saturation states.

A simple protocol was developed to measure seawater calcium carbonate saturation states (Ω) spectrophotometrically. Saturation states are typically derived from the separate measurement of two other carbon system parameters, with each requiring unique instrumentation and often complex measurement protocols. Using the new protocol, the only required equipment is a thermostatted laboratory spectrophotometer.

Spectrophotometric Determination of Carbonate Ion Concentrations: Elimination of Instrument-Dependent Offsets and Calculation of In Situ Saturation States.

This work describes an improved algorithm for spectrophotometric determinations of seawater carbonate ion concentrations ([CO]) derived from observations of ultraviolet absorbance spectra in lead-enriched seawater. Quality-control assessments of [CO] data obtained on two NOAA research cruises (2012 and 2016) revealed a substantial intercruise difference in average Δ[CO] (the difference between a sample's [CO] value and the corresponding [CO] value calculated from paired measurements of pH and dissolved inorganic carbon). Follow-up investigation determined that this discordance was due to the use of two different spectrophotometers, even though both had been properly calibrated.

Measuring ocean acidification: new technology for a new era of ocean chemistry.

Human additions of carbon dioxide to the atmosphere are creating a cascade of chemical consequences that will eventually extend to the bottom of all the world's oceans. Among the best-documented seawater effects are a worldwide increase in open-ocean acidity and large-scale declines in calcium carbonate saturation states. The susceptibility of some young, fast-growing calcareous organisms to adverse impacts highlights the potential for biological and economic consequences.

Baseline monitoring of the western Arctic Ocean estimates 20% of Canadian basin surface waters are undersaturated with respect to aragonite.

Marine surface waters are being acidified due to uptake of anthropogenic carbon dioxide, resulting in surface ocean areas of undersaturation with respect to carbonate minerals, including aragonite. In the Arctic Ocean, acidification is expected to occur at an accelerated rate with respect to the global oceans, but a paucity of baseline data has limited our understanding of the extent of Arctic undersaturation and of regional variations in rates and causes. The lack of data has also hindered refinement of models aimed at projecting future trends of ocean acidification.

In situ spectrophotometric measurement of dissolved inorganic carbon in seawater.

Autonomous in situ sensors are needed to document the effects of today's rapid ocean uptake of atmospheric carbon dioxide (e.g., ocean acidification).

Flow injection analysis of trace chromium (VI) in drinking water with a liquid waveguide capillary cell and spectrophotometric detection.

Hexavalent chromium (Cr(VI)) is an acknowledged hazardous material in drinking waters. As such, effective monitoring and assessment of the risks posed by Cr(VI) are important analytical objectives for both human health and environmental science. However, because of the lack of highly sensitive, rapid, and simple procedures, a relatively limited number of studies have been carried out in this field.

Evaluation of reagentless pH modification for in situ ocean analysis: determination of dissolved inorganic carbon using mass spectrometry.

Rationale: In situ analytical techniques that require the storage and delivery of reagents (e.g., acidic or basic solutions) have inherent durability limitations.

Spectrophotometric measurement of calcium carbonate saturation states in seawater.

Measurements of ocean pH and carbonate ion concentrations in the North Pacific and Arctic Oceans were used to determine calcium carbonate saturation states (Ω(CaCO(3))) from spectrophotometric methods alone. Total carbonate ion concentrations, [CO(3)(2-)](T), were for the first time at sea directly measured using Pb(II) UV absorbance spectra. The basis of the method is given by the following: [formula see text] where (CO(3))β(1) is the PbCO(3)(0) formation constant, e(i) are molar absorptivity ratios, and R = (250)A/(234)A (ratio of absorbances measured at 250 and 234 nm).

Determination of nanomolar chromate in drinking water with solid phase extraction and a portable spectrophotometer.

Determination of chromate at low concentration levels in drinking water is an important analytical objective for both human health and environmental science. Here we report the use of solid phase extraction (SPE) in combination with a custom-made portable light-emitting diode (LED) spectrophotometer to achieve detection of chromate in the field at nanomolar levels. The measurement chemistry is based on a highly selective reaction between 1,5-diphenylcarbazide (DPC) and chromate under acidic conditions.

Spectrophotometric calibration of pH electrodes in seawater using purified m-cresol purple.

This work examines the use of purified meta-cresol purple (mCP) for direct spectrophotometric calibration of glass pH electrodes in seawater. The procedures used in this investigation allow for simple, inexpensive electrode calibrations over salinities of 20-40 and temperatures of 278.15-308.

Flow injection analysis of nanomolar silicate using long pathlength absorbance spectroscopy.

Determination of silicate at low concentrations (i.e., nanomolar levels) is an important analytical objective for both marine science and the semiconductor industry.

Purification and characterization of meta-cresol purple for spectrophotometric seawater pH measurements.

Spectrophotometric procedures allow rapid and precise measurements of the pH of natural waters. However, impurities in the acid-base indicators used in these analyses can significantly affect measurement accuracy. This work describes HPLC procedures for purifying one such indicator, meta-cresol purple (mCP), and reports mCP physical-chemical characteristics (thermodynamic equilibrium constants and visible-light absorbances) over a range of temperature (T) and salinity (S).

Field-deployed underwater mass spectrometers for investigations of transient chemical systems.

The mass spectrometer developments and underwater deployments described in this work are directed toward observations of important reactive and influential inorganic and organic chemicals. Mass spectrometer systems for measurement of dissolved gases and volatile hydrocarbons were created by coupling a membrane analyte-introduction system with linear quadrupole and ion trap mass analyzers. For molecular masses up to 100amu, the in situ quadrupole system has detection limits on the order of 1-5ppb.

Long pathlength absorbance spectroscopy: trace copper analysis using a 4.4 m liquid core waveguide.

Procedures are described for measurement of dissolved copper with long pathlength Teflon AF-2400 liquid core waveguides. Using a 4.4 m waveguide, absorbance versus concentration is linear for copper concentrations between 1 and 160 nM.

Calibration of an in situ membrane inlet mass spectrometer for measurements of dissolved gases and volatile organics in seawater.

Use of membrane inlet mass spectrometers (MIMS) for quantitative measurements of dissolved gases and volatile organics over a wide range of ocean depths requires characterization of the influence of hydrostatic pressure on the permeability of MIMS inlet systems. To simulate measurement conditions in the field, a laboratory apparatus was constructed for control of sample flow rate, temperature, pressure, and the concentrations of a variety of dissolved gases and volatile organic compounds. MIMS data generated with this apparatus demonstrated thatthe permeability of polydimethylsiloxane (PDMS) membranes is strongly dependent on hydrostatic pressure.

Phytoplankton carbon fixation gene (RuBisCO) transcripts and air-sea CO(2) flux in the Mississippi River plume.

River plumes deliver large quantities of nutrients to oligotrophic oceans, often resulting in significant CO(2) drawdown. To determine the relationship between expression of the major gene in carbon fixation (large subunit of ribulose-1,5-bisphosphate carboxylase/oxygenase, RuBisCO) and CO(2) dynamics, we evaluated rbcL mRNA abundance using novel quantitative PCR assays, phytoplankton cell analyses, photophysiological parameters, and pCO(2) in and around the Mississippi River plume (MRP) in the Gulf of Mexico. Lower salinity (30-32) stations were dominated by rbcL mRNA concentrations from heterokonts, such as diatoms and pelagophytes, which were at least an order of magnitude greater than haptophytes, alpha-Synechococcus or high-light Prochlorococcus.

Simultaneous spectrophotometric flow-through measurements of pH, carbon dioxide fugacity, and total inorganic carbon in seawater.

An autonomous multi-parameter flow-through CO2 system has been developed to simultaneously measure surface seawater pH, carbon dioxide fugacity (fCO2), and total dissolved inorganic carbon (DIC). All three measurements are based on spectrophotometric determinations of solution pH at multiple wavelengths using sulfonephthalein indicators. The pH optical cell is machined from a PEEK polymer rod bearing a bore-hole with an optical pathlength of approximately 15 cm.

High-resolution in situ analysis of nitrate and phosphate in the oligotrophic ocean.

Accurate, high-resolution profiles of nitrate and phosphate distributions in the open ocean are difficult to obtain using conventional techniques. Concentrations typically range from low nanomolar levels in the stratified euphotic zone to micromolar levels below the nutricline. With multiple pumps, a heating cartridge, a long-path-length cell, and a multiwavelength spectrometer, the reconfigured Spectrophotometric Elemental Analysis System (SEAS) provides the capability to fully ascertain the distributions of nitrate and phosphate in the upper 200 m of the oligotrophic ocean.