Simultaneous vertical measurements of in situ pH and CO2 in the sea using spectrophotometric profilers

We have developed new systems capable of profiling to >1000 m for measuring in situ pH and fugacity of CO₂ (fCO₂) in the ocean using spectrophotometric analysis (pH and CO₂ profilers). The in situ pH is determined by detecting the color change of the pH indicator (m-cresol purple). It can withstand ambient pressure to 1000 m depth. The CO₂ profiler analyzed in situ fCO₂ by detecting the change of pH in an inner solution, equilibrated with the seawater through a gas permeable membrane. It can be operated to 2500 m depth. We used an amorphous fluoropolymer tubing form of AF-2400 for the gas permeable membrane due to its high gas permeability coefficients. The inner solution was a mixture of 2 μM bromocresol purple (BCP) and 5 μM sodium hydroxide. This system gave us a response time of 1 minute, which is twice as fast as previous systems. The precisions of pH and CO₂ profilers were within 0.002 and 2.5% respectively. We have used these profilers to study the North Pacific, obtaining good agreement with the difference between the data from profilers and a discrete bottle of 0.002 ± 0.005 pH (SE, n = 25) and −0.4 ± 3 μatm (SE, n = 31).     

Impurities in indicators used for spectrophotometric seawater pH measurements: Assessment and remedies

Spectrophotometric pH measurements have been widely used in oceanic CO₂−system research. However, impurities in indicator dyes from different manufacturers may cause uncertainty in measured pH values. In this work we report initial findings surrounding the potential significance of indicator sources (manufacturers) on pH measurements obtained with the sulfonephthalein indicator m-cresol purple. HPLC analyses were used for comparative assessments of impurities in m-cresol purple obtained from a range of manufacturers. Results indicate that m-cresol purple from different manufacturers, and perhaps from different batches of the same manufacturer, have different types and quantities of light-absorbing impurities. Impurities can contribute to pH offsets as large as 0.01 pH units. The pH offset caused by impurities decreases with decreasing sample pH. Indicators can be purified using preparative HPLC. Until purified indicators and refined indicator calibrations become available, we suggest that investigators should reserve some portion of each indicator batch for comparison with the properties of purified indicators.     

Spectrophotometric pH measurement in estuaries using thymol blue and m-cresol purple

The conditional acid dissociation constants (pK_a′) of two sulfonephthalein dyes, thymol blue (TB) and m-cresol purple (mCP), were assessed throughout the estuarine salinity range (0<S<40) using a tris/tris–HCl buffer and spectrophotometric measurement. The salinity dependence of the pK_a′ of both dyes was fitted to the equations (25 °C, total proton pH scale, mol kg soln⁻¹):

The estimated accuracy of pH measurements using these calculated pK_a′ values is considered to be comparable to that possible with careful use of a glass electrode (±0.01 pH unit) but spectrophotometric measurements in an estuary have the significant advantage that it is not necessary to calibrate an electrode at different salinities. pH was measured in an estuary over a tidal cycle with a precision of ±0.0005 pH unit at high (S>30) salinity, and ±0.002 pH unit at low (S<5) salinity. The pH increased rapidly in the lower salinity ranges (0<S<15) but less rapidly at higher salinities.     

The use of buffers to measure the pH of seawater

The pH of seawater can be measured in the field using potentiometric and spectrophotometric methods. The use of pH standards or buffers is an important aspect of the calibration of both methods in a laboratory on a common concentration scale. The buffers can also be used to monitor the performance of pH meter and spectrophotometer during a cruise. A procedure is described for the determination of the pH of seawater, where the proton concentration is expressed as moles kg-H₂O⁻¹ using seawater buffers. The buffers are prepared in synthetic seawater in the laboratory by the methods outlined by Bates and coworkers. We have prepared four buffers (Bis, Tris, Morpholine and 2-Aminopyridine) that cover a pH range from 6.8 to 8.8. The emf values of the buffers were measured with a H₂, Pt/AgCl, Ag electrode system after their preparation and bottling for use at sea. The measured emf values were found to be in good agreement (±0.05 mV) with the original measurements of Bates and coworkers from 0 to 45°C. The measured pH of these buffers are in good agreement (±0.001 pH units) with the values calculated from the equations of Dickson on the total pH scale based on Bates et al. Studies are underway to access the long term stability of these buffers. We have also used these buffers to calibrate systems used to make potentiometric and spectrophotometric measurements of pH on seawater relative to the H₂, Pt/Ag, AgCl electrode from 5 to 45°C.     

Impact of environmental factors on in situ determination of iron in seawater by flow injection analysis

A sensitive method for iron determination in seawater has been adapted on a submersible chemical analyser for in situ measurements. The technique is based on flow injection analysis (FIA) coupled with spectrophotometric detection. When direct injection of seawater was used, the detection limit was 1.6 nM, and the precision 7%, for a triplicate injection of a 4 nM standard. At low iron concentrations, on line preconcentration using a column filled with 8-hydroxyquinoline (8HQ) resin was used. The detection limit was 0.15 nM (time of preconcentration = 240 s), and the precision 6%, for a triplicate determination of a 1 nM standard, allowing the determination of Fe in most of the oceanic regimes, except the most depleted surface waters. The effect of temperature, pressure, salinity, copper, manganese, and iron speciation on the response of the analyser was investigated. The slope of the calibration curves followed a linear relation as a function of pressure (C_p = 2.8 × 10^{− 5}P + 3.4 × 10^{− 2} s nmol^{− 1}, R² = 0.997, for Θ = 13 °C) and an exponential relation as a function of temperature (C_Θ = 0.009e^0.103Θ, R² = 0.832, for P = 3 bar). No statistical difference at 95% confidence level was observed for samples of different salinities (S = 0, 20, 35). Only very high concentration of copper (1000 × [Fe]) produced a detectable interference. The chemical analyser was deployed in the coastal environment of the Bay of Brest to investigate the effect of iron speciation on the response of the analyser. Direct injection was used and seawater samples were acidified on line for 80 s. Dissolved iron (DFe, filtered seawater (0.4 μm), acidified and stored at pH 1.8) corresponded to 29 ± 4% of Fe_a (unfiltered seawater, acidified in line at pH 1.8 for 80 s). Most of Fe_a (71 ± 4%) was probably a fraction of total dissolvable iron (TDFe, unfiltered seawater, acidified and stored at pH 1.8).     

The contribution of atmospheric acid deposition to ocean acidification in the subtropical North Atlantic Ocean

The absorption of anthropogenic CO₂ and atmospheric deposition of acidity can both contribute to the acidification of the global ocean. Rainfall pH measurements and chemical compositions monitored on the island of Bermuda since 1980, and a long-term seawater CO₂ time-series (1983–2005) in the subtropical North Atlantic Ocean near Bermuda were used to evaluate the influence of acidic deposition on the acidification of oligotrophic waters of the North Atlantic Ocean and coastal waters of the coral reef ecosystem of Bermuda. Since the early 1980's, the average annual wet deposition of acidity at Bermuda was 15 ± 14 mmol m^− 2 year^− 1, while surface seawater pH decreased by 0.0017 ± 0.0001 pH units each year. The gradual acidification of subtropical gyre waters was primarily due to uptake of anthropogenic CO₂. We estimate that direct atmospheric acid deposition contributed 2% to the acidification of surface waters in the subtropical North Atlantic Ocean, although this value likely represents an upper limit. Acidifying deposition had negligible influence on seawater CO₂ chemistry of the Bermuda coral reef, with no evident impact on hard coral calcification.     

The effect of temperature on carbon dioxide partial pressures in seawater

A correction formula is theoretically derived to evaluate the change in partial pressure of carbon dioxide in seawater upon heating. The constraints on the heating process are constant salinity, total alkalinity, and total carbon dioxide concentration. The result is

Full-size image (1K)

. This equation fits δP_CO2/δt for open ocean seawater compositions to within approximately 9%. The almost constant 4.4%/°C effect is in agreement with that measured by Kanwisher (1960).     

自研高精度pH传感器的标定、校正方法及其在海水原位观测中的应用

电化学方法是测量海水pH值的主要方法之一。针对自主研发的基于铱金属及其氧化物电极的pH传感器,建立了海水环境下仪器标定和数据校正的方法,并在近岸和大洋环境中进行了原位测试的应用。仪器标定包括：(1)依照海水pH分析的标度要求选取适当的标定缓冲试剂;(2)以标准海水替代常用的2-氨基吡啶(AMP)溶液制备标定缓冲体系。数据校正主要包括温度背景校正及误差校正。海区原位测试应用以及与其他同类仪器对比表明,标定体系差异带来的误差可达1.00 pH单位,数据校正可提升测试精度0.10～3.00 pH单位不等。仪器的标定与数据校正方法能有效提高该自研pH传感器的测量精度。     

Total oxyradical scavenging capacity and cell membrane stability of haemocytes of the Arctic scallop, Chlamys islandicus, following benzo(a)pyrene exposure

Industrial activities, notably oil and gas industries, are expanding in the Arctic. Most of the biomarkers were developed using temperate organisms living at temperatures above 10 °C. Little is known about the biomarker responses of organisms living between −1.88 and 5 °C. Therefore, assessment of the toxicity of chemicals to cold-water adapted species is required. In this study, the Arctic scallop, Chlamys islandicus, was selected as a key species for bio-monitoring because of wide distribution in Arctic waters and its commercial value. Test animals, stored in seawater at 2 °C, were injected with benzo(a)pyrene (diluted in cod liver oil 5 mg ml⁻¹) in the adductor muscle every 24 h for four days giving a final dose of 0, 74 and 90.6 mg kg⁻¹ wet weight for control, low and high dose, respectively. The biomarkers used were total oxyradical scavenging capacity (TOSC) in the digestive gland and cell membrane stability of haemocytes. TOSC values were significantly reduced (ca. 30%) in exposed groups (P<0.05), indicating a depletion in oxyradical molecular scavengers. The antioxidant defences appeared to be overwhelmed by the reactive oxygen species as the plasma membranes of haemocytes were destabilised (P<0.05) probably due to lipid peroxidation. These data indicate that reactive oxygen species (ROS) were produced by Arctic scallops via the metabolisation of benzo(a)pyrene at 2 °C.     

Sodium hexametaphosphate as an aid in benthic sample sorting

The efficacy of sodium hexametaphosphate, when added to a formalin-Rose Bengal fixative solution, in improving the efficiency of benthic sample sorting by encouraging the disaggregation of silt-clay sediment has been investigated. Samples of estuarine mud (Mdφ = 6·1) from Damhead Creek, River Medway, were used for the analysis. A significant increase (23%; p < 0·01) in sieving efficiency was found in samples treated with concentrations of 1·24g/litre or more of sodium hexametaphosphate; treatments with higher concentrations than 1·24g/litre did not improve on this performance significantly. The use of 1·24g/litre sodium hexametaphosphate in an initial fixative/preservative solution is recommended as an economic and practical means of improving the efficiency of benthic sample sorting, without deleterious effects on the animal specimens in the sample.     

The influence of dissolved petroleum hydrocarbon residues on natural phytoplankton biomass

The effect of dissolved petroleum hydrocarbons in the environment on phytoplankton biomass measured as chlorophyll a was studied near the oil tanker route in the southern Bay of Bengal. In the transect from 5° N, 77° E to 5° N, 87° E the concentrations of dissolved petroleum hydrocarbons were negatively correlated with phytoplankton biomass, whereas in the 0° N, 87° E to 1° N, 79° E transect they were positively correlated with phytoplankton biomass. The mean petroleum hydrocarbon concentrations in the two transects were 12·12 ± 4·67 μg litre⁻¹ and 11·23 ± 4·5 μg litre⁻¹, respectively.It is surmised that the effect of dissolved petroleum hydrocarbons on phytoplankton biomass varies depending on the nature rather than the quantity of petroleum hydrocarbons present. Culture studies with unialgal Nitzschia sp. in seawater collected from selected stations in the study area as well as in artificial seawater spiked with the water-soluble petroleum hydrocarbon fraction of light Arabian Crude support this.     

Rates of oxygen transfer from air bubbles to aqueous NaCl solutions at various temperatures

Experiments have been conducted to investigate the effects of temperature on the interfacial surface area and on the rate of oxygen transfer from air bubbles dispersed in aqueous NaCl solutions. Tests were also conducted to estimate the effects of salt concentration on the size of the bubbles. In addition to NaCl solutions, seawater was used in some tests. The temperature effects were investigated at 5, 10, 15, 20, 25, and 30°C. The results showed a pronounced effect of the salt on the size of the bubbles, which first decreased sharply with increasing concentration, but showed no further drop when the concentration was increased beyond 0.6 M. Both in seawater and in the 0.6 M solution, the mass transfer rate, K_LA, increased almost linearly when temperature was increased within the range from 5 to 25°C. The salt solution, as well as the seawater, showed an increase of K_LA of 60–70% over that in pure water at the same temperatures. This effect was the result of increased surface area of bubbles because of decreased coalescence. The increase in surface area was strongly temperature dependent, especially between 15 and 20°C. Contrary to this behavior the surface area in pure water showed, practically, no temperature dependence. The results are explained and discussed on the basis of ion-water interactions.     

Long-term effect of beach replenishment on natural recovery of shallow Posidonia oceanica meadows

The recovery capacity of shallow Posidonia oceanica meadows degraded by beach replenishment eighteen years before was assessed in two impacted meadows and compared with other two undisturbed localities. Inside each locality, we selected randomly three sites separated by 500–1000 m. At site level we study the vitality of P. oceanica meadow assessing the vegetative growth, leaf characteristics, and non-structural carbohydrates of the plants. Additionally, at locality level, silt-clay fraction, organic matter, pH and light intensity incident on the sea bottom were measured to evaluate the environmental conditions. Covering of P. oceanica was significantly lower at the impacted localities while amount of dead “matte” was higher. Leaf production of horizontal rhizomes (14.6 ± 1.11 vs 19.47 ± 1.45 leaves y⁻¹), net total rhizomes recruitment (2.33 ± 0.17 vs 4.3 ± 0.33 branches y⁻¹) and starch concentration (43.625 ± 0.67 vs 54.45 ± 0.74 mg per g of rhizome) at impacted meadows were significantly lower than controls. Leaf features, epiphytes biomass, colonization, elongation and horizontal and vertical rhizome production did not show significant differences. Sediments at impacted localities contained higher silt-clay fraction and higher organic matter load while pH was lower. Light intensity on the sea bottom measured at all localities was over the minimum light requirements estimated for P. oceanica. Our results show that the press impact produced by beach replenishment was enduring in the time slowing natural recovery by 45%. This impact may be related with changes in the sediment features.     

The reliability of analytical data for tributyltin (TBT) in sea water and its implications on water quality criteria

To investigate the reliability of analytical data for tributyltin (TBT) in sea water, split water samples were distributed to ten laboratories in six countries. The sub-surface samples comprised: (i) an offshore (0·5 km) water sample, (ii) the same sample but spiked with an undisclosed quantity of TBT standard compound (175 ng TBT⁺ liter⁻¹), and (iii) a sample taken from a yacht marina. The seven acceptable data sets were in good agreement for the spiked sample (178 ± 26 ng TBT⁺ liter⁻¹) but showed a greater variation in concentrations reported for the yacht marina sample (366 ± 93 ng TBT⁺ liter⁻¹). Atomic absorption and gas chromatographic-flame photometric detection techniques produced results of similar accuracy and precision. Samples acidified with 1 ml of 10% (v/v) acetic acid appeared stable for more than 2 weeks when stored refrigerated and in darkness. Analyses of the offshore seawater sample revealed TBT contamination (9 ± 7 ng TBT⁺ liter⁻¹) indicating dispersion of the compound to the shelf waters off Monaco. The spread in values reported by the laboratories demonstrates inherent difficulties in obtaining good precision below approximately 20 ng TBT⁺ liter⁻¹. This observation is discussed with respect to the setting and enforcing of water quality standards.     

Shelf spawning habitat of Emmelichthys nitidus in south-eastern Australia – Implications and suitability for egg-based biomass estimation

The spawning habitat of Emmelichthys nitidus (Emmelichthyidae) in south-eastern Australia is described from vertical ichthyoplankton samples collected along the shelf region off eastern through to south-western Tasmania during peak spawning in October 2005–06. Surveys covered eastern waters in 2005 (38.8–43.5°S), and both eastern and southern waters in 2006 (40.5°S around to 43.5°S off the south-west). Eggs (n = 10,393) and larvae (n = 378) occurred along eastern Tasmania in both years but were rare along southern waters south and westwards of 43.5°S in 2006. Peak egg abundances (1950–2640 per m⁻²) were obtained off north-eastern Tasmania (40.5–41.5°S) between the shelf break and 2.5 nm inshore from the break. Eggs were up to 5-days old, while nearly 95% of larvae were at the early preflexion stage, i.e. close to newly emerged. Average abundances of aged eggs pooled across each survey declined steadily from day-1 to day-5 eggs both in 2005 (97-18) and 2006 (175-34). Moreover, day-1 egg abundances were significantly greater 2.5 nm at either side of the break, including at the break, than in waters ≥5 nm both inshore and offshore from the break. These results, complemented with egg and larval data obtained in shelf waters off New South Wales (NSW; 35.0–37.7°S) in October 2002–03, indicate that the main spawning area of E. nitidus in south-eastern Australia lies between 35.5°S off southern NSW and 43.5°S off south-eastern Tasmania, and that spawning activity declines abruptly south and westwards of 43.5°S around to the south-west coast. In addition, quotient analyses of day-1 egg abundances point to a preferred spawning habitat contained predominantly within a 5 nm corridor along the shelf break, where waters are 125–325 m deep and median temperatures 13.5–14.0 °C. Spawning off eastern Tasmania is timed with the productivity outburst typical of the region during the austral spring, and the temperature increase from the mixing between the southwards advancing, warm East Australian Current and cooler subantarctic water over the shelf. Overall, ichthyoplankton data, coupled with reproductive information from adults trawled off Tasmania, indicate that E. nitidus constitutes a suitable species for the application of the daily egg production method (DEPM) to estimate spawning biomass. This finding, together with evidence in support of a discrete eastern spawning stock extending from southern NSW to southern Tasmania, strengthens the need for DEPM-based biomass estimates of E. nitidus prior to further fishery expansion.     

Semi-empirical equations for the partial molar volumes of some ions in water and in seawater

Partial molar volumes of the major salts of seawater found in diluted seawater and in pure water are experimentally determined at temperatures of 5°C, 15°C and 25°C. The range of salinity investigated, which is not purely oceanographic, is the link between pure water and seawater in the World Ocean.The partial molar volumes were determined by using the procedure of Poisson and Chanu (1976). An empirical relation is given, linking the partial molar volumes of the salts or major ions of seawater in pure water with those measured in seawater, within the salinity range 0–40 g kg⁻¹ and the temperature range 0–25°C.     

The diffusion coefficient of dissolved silica revisited

The diffusion coefficient of dissolved silica was determined for two different salinities, 36 and 0, at temperatures ranging from 2 °C to 30 °C and at an average pH value of 8.1. Our results show limited influence of salinity and a variation by a factor of 2 to 3 of the silica diffusion coefficient within the temperature range considered in this study. The values obtained at 25 °C are in agreement with previous work carried out at room temperature for seawater and freshwater. The dependency on temperature and viscosity of the diffusion coefficient agrees well with the Einstein–Stokes equation. The composition of the solvent appears to be an important factor because it modifies the viscosity and allows for the complexation of the dissolved silica with less mobile ions, while its pH controls the dissolved silica speciation. In seawater, the higher viscosity and the presence of dissociated and polymeric species result in a decrease of the diffusion coefficient compared to freshwater systems.     

Trichodesmium erythraeum (Ehrenberg) bloom along the southwest coast of India (Arabian Sea) and its impact on trace metal concentrations in seawater

The incidence of a large scale Trichodesmium erythraeum bloom along the southwest coast of India (Arabian Sea) observed in May 2005 is reported. Around 4802 filaments of T. erythraeum ml⁻¹ seawater was observed and a colony consisted of 3.6 × 10⁵ cells. The bloom was predominant off Suratkal (12° 59′N and 74° 31′E) with a depth of about 47 m, covering an area of 7 km in length and 2 km width. The concentrations of Zinc, Cadmium, Lead, Copper, Nickel and Cobalt were determined in samples collected from the bloom and non-bloom sites using stripping voltammetry. The observed hydrographical and meteorological parameters were found to be favorable for the bloom. The concentrations of Zinc, Cadmium and Nickel were found to be higher at bloom stations, while the concentrations of Lead, Copper and Cobalt were found to be very low at bloom stations. Elevated concentrations of Cadmium and Cobalt were observed at Valappad mainly due to the decomposition of detrital material produced in the bloom. Statistically significant differences (P > 0.01) in metal concentrations between the bloom and non-bloom stations were not observed except for Copper. Metals such as Lead, Copper and Cobalt were removed from the seawater at all places where bloom was observed. Cadmium was found to be slowly released during the decaying process of the bloom.     

Effects of alkaline aluminate waste dumping on seawater chemistry

The alkaline aluminate waste, of which 1000–2000 tonnes are dumped a few times a year off the Belgian coast in the Southern Bight of the North Sea, contains 5·4% NaCl, 1·8% dissolved Al and 7·4% NaOH, in addition to traces of heavy metals and some aniline- and phenol-derivatives. The pH rises locally to 8-5 and the total Al-concentration reaches 120niglitre⁻¹(corresponding to an initial waste dilution factor of only 150) in the 10-m wide track just beyond the discharging barge, but these decay quickly to pH 8·1 and 1 mg litre^-1 in the 30-m wide track, 500m behind the barge. The relation between the waste concentration and seawater pH was studied. The white precipitate that forms immediately in the sea was identified as Mg₆---Al₂---CO₃---(OH)₁₆---4H₂0 (hydrotalcite-manasseite like). No trace of it was found in the local sediments.