Measurement of dissolved oxygen using optodes in a FerryBox system

Optode sensors can provide detailed information on concentrations of dissolved oxygen, which in turn may be used to quantify variations in net primary productivity. Throughout 2005 and 2006 the performance of commercially available oxygen optodes was examined, one in each year. The optode was part of an autonomous measurement system (FerryBox) on a ferry operating between Portsmouth (UK) and Bilbao (Spain). On crossings during which water samples were collected manually, the optode outputs were compared to measurements of dissolved oxygen made by Winkler titrations. The optodes maintained good stability with no evidence of instrumental drift during the course of a year. Over the observed concentration range (230–330 mM m⁻³) the optode data were approximately 2% low in both years. By fitting the optode data to the Winkler data the median difference between the optode and Winkler measurements is reduced to less than 1 mM m⁻³ (0.3%) in both years. The most appropriate calibration factor for 2005 was corrected O₂ = Optode O₂ × 1.018 and for 2006 the corresponding equation is corrected O₂ = Optode O₂ × 0.884 + 36.8. The standard deviation (95%) of the difference between the individual Winkler measurements was 5 mM m⁻³ and 3 mM m⁻³ in 2005 and 2006 respectively.Calculation of the oxygen saturation anomaly is required for calculation of the air sea exchange of oxygen and net biological production. This calculation requires the use of both salinity and temperature data. Salinity is measured to better than 0.1 so the corresponding error in anomaly is less than 0.2 mM m⁻³. Distortion of the temperature data is present due to warming of the water pumped to the optode. In winter this warming at the optode may be as great as 0.4 °C. The difference in the pumped water temperature can be corrected for by reference to other measurements of sea surface temperature reducing the error to less than 1 mM m⁻³.     

Winkler's method overestimates dissolved oxygen in seawater: Iodate interference and its oceanographic implications

Dissolved oxygen in seawater has been determined by using the Winkler's reaction scheme for decades. An interference in this reaction scheme that has been heretofore overlooked is the presence of naturally occurring iodate in seawater. Each mole of iodate can result in an apparent presence of 1.5 mol of dissolved oxygen. At the concentrations of iodate in the surface and deep open ocean, it can lead to an overestimation of 0.52 ± 0.15 and 0.63 ± 0.05 μmol kg^− 1 of oxygen in these waters respectively. In coastal and inshore waters, the effect is less predictable as the concentration of iodate is more variable. The solubility of oxygen in seawater was likely overestimated in data sources that were based on the Winkler's reaction scheme for the determination of oxygen. The solubility equation of García and Gordon [Garcia H.E., Gordon, L.I., 1992. Oxygen solubility in seawater: Better fitting equations. Limnol. Oceanogr. 37, 1307–1312] derived from the results of Benson and Krause [Benson, F.B., Krause, D. Jr., 1984. The concentration and isotopic fractionation of oxygen dissolved in freshwater and seawater in equilibrium with the atmosphere. Limnol. Oceanogr. 29, 620–632] is free from this source of error and is recommended for general use. By neglecting the presence of iodate, the average global super-saturation of oxygen in the surface oceans and the corresponding efflux of oxygen to the atmosphere both have been overestimated by about 8%. Regionally, in areas where the degree of super-saturation or under-saturation of oxygen in the surface water is small, such as in the tropical oceans, the net air–sea exchange flux can be grossly under- or overestimated. Even the estimated direction of the exchange can be reversed. Furthermore, the presence of iodate can lead to an overestimation of the saturation anomaly of oxygen in the upper ocean attributed to biological production by 0.23 ± 0.07%. AOU may have been underestimated by 0.52 ± 0.15 and 0.63 ± 0.05 μmol kg^− 1 in the surface mixed layer and deep water, while preformed phosphate and preformed nitrate may have been overestimated by 0.004 ± 0.001 and 0.06 ± 0.02 μmol kg^− 1 in the surface mixed layer, and 0.005 ± 0.0004 and 0.073 ± 0.006 μmol kg^− 1 in the deep water. These are small but not negligible corrections, especially in areas where the values of these parameters are small. At the increasing level of sophistication in the interpretation of oxygen data, this source of error should now be taken into account. Nevertheless, in order to avoid confusion, an internationally accepted standard needs to be adopted before these corrections can be applied.     

A method to measure the isotopic (C) composition of dissolved organic carbon using a high temperature combustion instrument

The stable isotopes of dissolved organic carbon (DOC) are a powerful tool for distinguishing sources and inputs of organic matter in aquatic systems. While several methods exist to perform these analyses, no labs routinely utilize a high temperature combustion (HTC) instrument. Advantages of HTC instruments include rapid analysis, small sample volumes and minimal sample preparation, making them the favored devices for most routine oceanic DOC concentration measurements. We developed a stable carbon DOC method based around an HTC system. This method has the benefit of a simple setup, requiring neither vacuum nor high pressures. The main drawback of the method is a significant blank, requiring careful accounting of all blank sources for accurate isotopic and concentration values. We present here a series of experiments to determine the magnitude, source and isotopic composition of the HTC blank. Over time, the blank is very stable at  20 ng of carbon with a δ¹³C of − 18.1‰ vs. VPDB. The similarity of the isotopic composition of the blank and seawater samples makes corrections relatively minor. The precision of the method was determined by oxidizing organic standards with a wide isotopic and concentration range (− 9‰ to − 39‰; 18 μM to 124 μM). Analysis of seawater samples demonstrates the accuracy for low concentration, high salinity samples. The overall error on the measurement is approximately ± 0.8‰.     

Vertical and horizontal distribution of fluorescent dissolved organic matter in the Southern Ocean

The vertical and horizontal distribution of fluorescent dissolved organic matter (FDOM), determined by fluorescence intensity at 320 nm excitation and 420 nm emission, were clarified in nine stations on two transects at the Southern Ocean, including a subtropical, subantarctic, polar frontal and Antarctic zone. All vertical profiles of fluorescence intensity showed that levels were lowest in the surface waters, increased with increasing the depth in mid-depth waters ( 2000 m), and then stayed within a relatively narrow range from there to the bottom. Such vertical profiles of FDOM were similar to those of nutrients, but were adverse to dissolved oxygen. In water columns below the temperature-minimum subsurface water (dichothermal waters) in the Antarctic zone and below the winter mixed layer in the other zones, we determined the relationships of fluorescence intensity to concentrations of nutrients and apparent oxygen utilization (AOU) over the entire area of the present study, and found significant linear correlations between the levels of fluorescence intensity and nutrient concentrations (r =  0.70 and 0.71 for phosphate and nitrate + nitrite, respectively) and AOU (r = 0.91). From the strong correlation coefficient between fluorescence intensity and AOU, we concluded that FDOM in the Southern Ocean is formed in situ via the biological oxidation of organic matter. The regeneration of the nutrients/consumption of the oxygen/formation of FDOM was active in mid-depth waters. However, the correlations between fluorescence intensities and nutrients and AOU were different in the mid-depth water masses, Subantarctic Mode Water (SAMW), and Antarctic Intermediate Water (AAIW), indicating that the sources of organic matter responsible for FDOM formation were different. A considerable amount of FDOM in the SAMW is thought to be produced by the remineralization of DOM in addition to sinking particulate organic matter, while DOM is less responsible for FDOM formation in the AAIW.     

柘林湾水体溶解氧的分布特征及其与营养盐的关系

根据2001年7月～2002年7月间对柘林湾进行的溶解氧和营养盐含量的调查数据,探讨柘林湾海域溶解氧的时空分布规律及其与营养盐之间的相关关系.结果表明柘林湾的溶解氧含量年均值为5.88mg/dm^3,呈河口、湾外高,湾内低的平面分布规律.回归分析表明,柘林湾溶解氧含量与NO3-N含量呈显著的正相关关系,与PO4-P、NH3-N含量呈显著的负相关关系.大规模的养殖生产是影响柘林湾水体DO含量的一个重要因素.     

Avoidance behaviour of freshwater fish and shrimp exposed to ammonia and low dissolved oxygen separately and in combination

Abstract

The responses of common smelt (Retropinna retropinna Richardson), inanga (Galaxias maculatus Jenyns), common bully (Gobiomorphus cotidianus McDowall), and shrimp (Paratya curvirostris Heller) to ammonia and low dissolved oxygen (DO), separately and in combination, were measured in a fluvarium. Only common smelt avoided high or low ammonia (c. 8.5 and 2.0 g m^?3 NH3, respectively) and low DO (c. 2 g m^?3) alone and in combination. Shrimp avoided high ammonia and low DO+ammonia but not low DO on its own. Inanga and bullies showed no significant negative response to either contaminant; rather, inanga were strongly attracted to low ammonia and bullies to low DO. These results parallel those from toxicity experiments that show common smelt and shrimp are usually among the most sensitive native species to various contaminants. The consistent and appropriate avoidance behaviour shown by common smelt, in particular, suggests this species would be a good indicator organism for assessing the health of lowland waterways.     

长江口及邻近海域表层水体溶解氧饱和度的季节变化和特征

根据“908”ST04区块调查的夏、冬、春、秋季四个航次和“908”补充调查的8月航次资料对长江口及邻近海区表层水体溶解氧及其饱和度进行了探讨.研究表明东海北部表层水体在夏季和春季以浮游植物光合作用为主要控制过程,特别是7、8月份长江口外、杭州湾外及浙江近海存在大范围的强光合作用区;秋季以有机质氧化分解过程为主,表层溶...     

A simple method for calibrating optical backscatter sensors in high concentrations of non-cohesive sediments

A new method is introduced for calibrating optical backscatter sensors for suspended quartz sand concentrations of up to 200 kg m⁻³. Due to the high settling velocity of quartz sand in water, considerable difficulties have arisen in the past to maintain a spatially and temporally homogeneous suspension suitable for calibration. Traditional methods are clumsy and prone to errors. Here, the sediment is calibrated in glycerol, a clear fluid with a higher viscosity than water. The settling velocity is reduced by three orders of magnitude. An empirical relationship is obtained which is used to correct for any optical differences in response of the sensors in the two fluids. Any extra errors introduced by calibrating with a different fluid from that found in the field are outweighed by the simplicity and reliability of this method.     

The summertime net transport of dissolved oxygen,salt and heat in a salt marsh basin,North Inlet,S.C.

This study addresses the impact marshes have on the dissolved oxygen content of tidal waters, particularly during summer when respiratory demand for oxygen in adjacent coastal waters is at a maximum and the solubility of oxygen is lowest. The net transports of dissolved oxygen, salt and heat have been measured for 65 tidal cycles during late spring and summer for a small (0·14 km²) salt marsh basin near North Inlet, S.C. The results indicate that export of dissolved oxygen occurs only on tidal cycles that begin between 2:00 am and 10:00 am such that high tide occurs within 4 h of noon. The largest exports of oxygen and heat are produced by spring tides beginning near sunrise. Although the time window for oxygen export is only about 8 h in duration, there is a more or less overall long-term balance between export and import because the magnitude of oxygen export is about 25% greater than import. The magnitude of heat export similarly exceeds heat import but because the time windows for heat export and import are equal, there is an overall export of heat. This study thus suggests that in summer salt marshes of the Atlantic coast export heat and are in balance with respect to the export and import of dissolved oxygen. However, because of the interaction of the diurnal tide with the daily cycle of solar radiation, transient dissolved oxygen concentrations in tidal waters can range from 1.5 to 10.0 ppm. Thus loading of additional oxygen consuming materials to these waters possibly could lead to significant periods of anoxia.     

Development of a fluorescence quenching assay to measure the fraction of organic carbon present in self-assembled gels in seawater

The dissolved organic carbon pool (DOC) is among the largest reservoir of reduced carbon on our planet. The demonstration that DOC polymers remain in assembly/dispersion equilibrium forming microscopic hydrogels has a broad range of critical implications. Previous studies estimate that  10% of DOC could be assembled as gels, yielding values of  7 × 10¹⁶ g of organic carbon present as microscopic hotspots of high substrate concentration. This huge mass of reduced carbon emphasizes the need to develop reliable methods to systematically investigate the budget of self-assembled marine gels (SAG), and their role in biogeochemical cycling. However, a quantitative method to measure SAG in seawater has not been available. Here we present the validation of a simple assay to measure the mass of organic carbon assembled as microgels in native seawater. This method is based on the ratio of Chlortetracycline (CTC) fluorescence quenching between Ca bound to non-assembled organic molecules and molecules assembled as microgels. This assay can be readily implemented on board using a low cost fluorometer and provisions to measure TOC.     

Application of potentiometric method using a cell without liquid junction to underway pH measurements in surface seawater

This study evaluated a method to carry out underway pH measurements of surface seawater by means of a cell without liquid junction using glass electrodes for hydrogen and sodium ions as follows:

Glass-electrode-Na+

Test solution (reference solution)

H+-glass-electrode

Full-size table

Table options

     

12.

Phytoplankton driven distribution of dissolved and particulate lipids in a semi-enclosed temperate sea (Mediterranean): Spring to summer situation     

Sanja Frka  Blaženka Gašparović  Daniela Marić  Jelena Godrijan  Tamara Djakovac  Vjeročka Vojvodić  Jelena Dautović  Zlatica Kozarac 《Estuarine, Coastal and Shelf Science》2011

The relationship between changes in lipid classes and phytoplankton composition and abundance in the northern Adriatic was studied during spring and summer 2008 at two stations with different nutrient levels, i.e. at the western mesotrophic and eastern oligotrophic areas. Changes in the phytoplankton community depended on temporal surface nutrient depletion and bottom accumulation; that is, microphytoplankton, mainly diatoms Pseudo-nitzschia sp., developed at nutrient richer surface layers of the mesotrophic area in spring and at deeper layers of the oligotrophic site in late summer. In other periods nanophytoplankton dominated. Dissolved organic carbon (DOC) and lipid content were comparable for the two stations, while particulate organic carbon (POC) was richer at the mesotrophic side. Total lipid concentrations varied in the range from 8.0 to 92.2 μg l⁻¹ and from 16.9 to 76.9 μg l⁻¹ in the dissolved and particulate fractions, respectively. DOC and POC contents were in the ranges from 0.77 to 1.58 mg l⁻¹ and from 0.06 to 0.56 mg l⁻¹, respectively. Lipid and organic carbon distribution did not follow phytoplankton progression, indicating decoupling between organic matter production and decomposition throughout the investigation period. The main sources of lipids were marine phytoplankton and bacteria. Low nutrient conditions caused increased biosynthesis of lipids. Also, increasing oligotrophy led to an increasing number of phytoplankton taxa. The synthesis and accumulation of glycolipids by the developed taxa were enhanced during nutrient exhaustion, contributing in late summer, on average, 20.2 and 22.0% at the mesotrophic and oligotrophic stations, respectively, in the particulate fraction. The distribution of bacterial lipids and lipid breakdown products implies that bacterial lipid degradation was significant in spring, while very probably lipid abiotic degradation took place during summer.     

13.

Fine hydrochemical structure of the redox zone in the black sea according to the results of measurements with an open oxygen sensor and with bottle samplers     

P. A. Stunzhas  E. V. Yakushev 《Oceanology》2006,46(5):629-641

This study is based on the data obtained on July 14–17, 2004 over a section across the coastal anticyclonic eddy near the town of Tuapse. The data on the oxygen distribution obtained by the Winkler procedure and with an open (membrane-free) sensor with a 15-cm spatial resolution were compared. The divergence of the results in the lower part of the oxycline was 3 μmol or lower; the sensor error was estimated as 1 μmol. The previous data on the absence of the layer of oxygen and hydrogen sulfide coexistence were confirmed. It was shown that the lower boundary of oxygen permeation (where its concentration appeared to be below 1.0 μmol) closely coincided with the upper boundary of the bivalent manganese occurrence, because their coexistence layer was 1 ± 1 m in thickness. Within the same layer or 1–2 m above it, the upper boundary of the deep-sea ammonium and the phosphate minimum were situated. These data may be treated in the following way: oxygen is completely utilized for the oxidation of ammonia and bivalent manganese, and the oxidized suspended manganese formed sinks and is utilized in the reactions of hydrogen sulfide oxidation. The role of the near-slope downwelling (the supply of oxygen-enriched waters to the layers close to the redox zone), which was also observed in the cross section, is discussed.     

14.

Variation reduction in quality of an optical triangulation system employed for underwater range finding     

Hsin-Hung Chen   《Ocean Engineering》2002,29(15):1011-1893

This paper attempts to more thoroughly understand the factor effects on the performance of an optical triangulation system used for range finding in water. In this study analytical expressions for estimating the peak of the laser spot and for image processing were presented. Both the design of experiment process and the Taguchi method have been used to evaluate factor effects and to specify design parameters. To assess the effects of monochrome and color image displays on the performance of range finding, two sets of experiments were carried out. The optimum models based on factor effects were predicted and constructed through the analysis of variance. The confirmation experiments were performed and the outcomes are in good agreement with the predicted optima. Based upon the results of experiments and analyses, it is found that brightness, contrast, and peak detection algorithms are the main factors to dominate the quality of range finding while using a monochrome camera. And further, all control factors of brightness, contrast, peak detection algorithm, sampling range, and specific primary color for intensity computation are critical to the quality of range finding while using a color camera. Notably, right selections of the image resolution and the sampling range can shorten the computing time and get high precision results.     

15.

The beam attenuation to chlorophyll ratio: an optical index of phytoplankton physiology in the surface ocean?   总被引：1，自引：0，他引：1  

Michael J. Behrenfeld  Emmanuel Boss 《Deep Sea Research Part I: Oceanographic Research Papers》2003,50(12):1537-1549

The particulate beam attenuation coefficient (c_p) is proportional to the concentration of suspended particles in a size domain overlapping that of the phytoplankton assemblage. c_p is largely insensitive to changes in intracellular chlorophyll concentration, which varies with growth irradiance (a process termed ‘photoacclimation’). Earlier studies have shown that the ratio of c_p:chlorophyll (i.e., c_p^*) exhibits depth-dependent changes that are consistent with photoacclimation. Similar relationships may likewise be expected in the horizontal and temporal dimensions, reflecting changes in mixing depth, incident irradiance, and light attenuation. A link between c_p^* and more robust photoadaptive variables has never been explicitly tested in the field. Here we use five historical field data sets to directly compare spatial and temporal variability in c_p^* with two independent indices of photoacclimation: the light-saturated, chlorophyll-normalized photosynthetic rate, P^b_opt, and the light-saturation index, E_k. For the variety of oceanographic conditions considered, a first-order correlation emerged between c_p^* and P^b_opt or E_k. These simple empirical results suggest that a relationship exists between a bio-optical variable that can potentially be retrieved remotely (c_p^*) and physiological variables crucial for estimating primary productivity in the sea.     

Phytoplankton driven distribution of dissolved and particulate lipids in a semi-enclosed temperate sea (Mediterranean): Spring to summer situation

The relationship between changes in lipid classes and phytoplankton composition and abundance in the northern Adriatic was studied during spring and summer 2008 at two stations with different nutrient levels, i.e. at the western mesotrophic and eastern oligotrophic areas. Changes in the phytoplankton community depended on temporal surface nutrient depletion and bottom accumulation; that is, microphytoplankton, mainly diatoms Pseudo-nitzschia sp., developed at nutrient richer surface layers of the mesotrophic area in spring and at deeper layers of the oligotrophic site in late summer. In other periods nanophytoplankton dominated. Dissolved organic carbon (DOC) and lipid content were comparable for the two stations, while particulate organic carbon (POC) was richer at the mesotrophic side. Total lipid concentrations varied in the range from 8.0 to 92.2 μg l⁻¹ and from 16.9 to 76.9 μg l⁻¹ in the dissolved and particulate fractions, respectively. DOC and POC contents were in the ranges from 0.77 to 1.58 mg l⁻¹ and from 0.06 to 0.56 mg l⁻¹, respectively. Lipid and organic carbon distribution did not follow phytoplankton progression, indicating decoupling between organic matter production and decomposition throughout the investigation period. The main sources of lipids were marine phytoplankton and bacteria. Low nutrient conditions caused increased biosynthesis of lipids. Also, increasing oligotrophy led to an increasing number of phytoplankton taxa. The synthesis and accumulation of glycolipids by the developed taxa were enhanced during nutrient exhaustion, contributing in late summer, on average, 20.2 and 22.0% at the mesotrophic and oligotrophic stations, respectively, in the particulate fraction. The distribution of bacterial lipids and lipid breakdown products implies that bacterial lipid degradation was significant in spring, while very probably lipid abiotic degradation took place during summer.     

Fine hydrochemical structure of the redox zone in the black sea according to the results of measurements with an open oxygen sensor and with bottle samplers

This study is based on the data obtained on July 14–17, 2004 over a section across the coastal anticyclonic eddy near the town of Tuapse. The data on the oxygen distribution obtained by the Winkler procedure and with an open (membrane-free) sensor with a 15-cm spatial resolution were compared. The divergence of the results in the lower part of the oxycline was 3 μmol or lower; the sensor error was estimated as 1 μmol. The previous data on the absence of the layer of oxygen and hydrogen sulfide coexistence were confirmed. It was shown that the lower boundary of oxygen permeation (where its concentration appeared to be below 1.0 μmol) closely coincided with the upper boundary of the bivalent manganese occurrence, because their coexistence layer was 1 ± 1 m in thickness. Within the same layer or 1–2 m above it, the upper boundary of the deep-sea ammonium and the phosphate minimum were situated. These data may be treated in the following way: oxygen is completely utilized for the oxidation of ammonia and bivalent manganese, and the oxidized suspended manganese formed sinks and is utilized in the reactions of hydrogen sulfide oxidation. The role of the near-slope downwelling (the supply of oxygen-enriched waters to the layers close to the redox zone), which was also observed in the cross section, is discussed.     

Variation reduction in quality of an optical triangulation system employed for underwater range finding

This paper attempts to more thoroughly understand the factor effects on the performance of an optical triangulation system used for range finding in water. In this study analytical expressions for estimating the peak of the laser spot and for image processing were presented. Both the design of experiment process and the Taguchi method have been used to evaluate factor effects and to specify design parameters. To assess the effects of monochrome and color image displays on the performance of range finding, two sets of experiments were carried out. The optimum models based on factor effects were predicted and constructed through the analysis of variance. The confirmation experiments were performed and the outcomes are in good agreement with the predicted optima. Based upon the results of experiments and analyses, it is found that brightness, contrast, and peak detection algorithms are the main factors to dominate the quality of range finding while using a monochrome camera. And further, all control factors of brightness, contrast, peak detection algorithm, sampling range, and specific primary color for intensity computation are critical to the quality of range finding while using a color camera. Notably, right selections of the image resolution and the sampling range can shorten the computing time and get high precision results.     

The beam attenuation to chlorophyll ratio: an optical index of phytoplankton physiology in the surface ocean?

The particulate beam attenuation coefficient (c_p) is proportional to the concentration of suspended particles in a size domain overlapping that of the phytoplankton assemblage. c_p is largely insensitive to changes in intracellular chlorophyll concentration, which varies with growth irradiance (a process termed ‘photoacclimation’). Earlier studies have shown that the ratio of c_p:chlorophyll (i.e., c_p^*) exhibits depth-dependent changes that are consistent with photoacclimation. Similar relationships may likewise be expected in the horizontal and temporal dimensions, reflecting changes in mixing depth, incident irradiance, and light attenuation. A link between c_p^* and more robust photoadaptive variables has never been explicitly tested in the field. Here we use five historical field data sets to directly compare spatial and temporal variability in c_p^* with two independent indices of photoacclimation: the light-saturated, chlorophyll-normalized photosynthetic rate, P^b_opt, and the light-saturation index, E_k. For the variety of oceanographic conditions considered, a first-order correlation emerged between c_p^* and P^b_opt or E_k. These simple empirical results suggest that a relationship exists between a bio-optical variable that can potentially be retrieved remotely (c_p^*) and physiological variables crucial for estimating primary productivity in the sea.