Burkhard Horstkotte

Changes in the C, N, and P cycles by the predicted salps-krill shift in the southern ocean

The metabolic carbon requirements and excretion rates of three major zooplankton groups in the Southern Ocean were studied in February 2009. The research was conducted in the framework of the ATOS research project as part of the Spanish contribution to the International Polar Year. The objective was to ascertain the possible consequences of the predicted zooplankton shift from krill to salps in the Southern Ocean for the cycling of biogenic carbon and the concentration and stoichiometry of dissolved inorganic nutrients. The carbon respiratory demands and NH4-N and PO4-P excretion rates of < 5 mm size copepods, krill and salps were estimated by incubation experiments. The carbon-specific metabolic rates and N:P metabolic quotients of salps were higher than those of krill (furcilia spp. and adults) and copepods, and as expected there was a significant negative relation between average individual zooplankton biomass and their metabolic rates, each metabolic process showing a particular response that lead to different metabolic N:P ratios. The predicted change from krill to salps in the Southern Ocean would encompass not only the substitution of a pivotal group for Antarctic food webs (krill) by one with an indifferent trophic role (salps). In a zooplankton community dominated by salps the respiratory carbon demand by zooplankton will significantly increase, and therefore the proportion of primary production that should be allocated to compensate for the global respiratory C-losses of zooplankton. At the same time, the higher production by salps of larger, faster sinking fecal pellets will increase the sequestration rate of biogenic carbon. Similarly, the higher N and P excretion rates of zooplankton and the changes in the N:P stoichiometry of the metabolic products will modify the concentration and proportion of N and P in the nutrient pool, inducing quantitative and qualitative changes on primary producers that will translate to the whole Southern Ocean ecosystem.

An environmental friendly method for the automatic determination of hypochlorite in commercial products using multisyringe flow injection analysis

A multisyringe flow injection analysis system was used for the determination of hypochlorite in cleaning agents, by measurement of the native absorbance of hypochlorite at 292 nm. The methodology was based on the selective decomposition of hypochlorite by a cobalt oxide catalyst giving chloride and oxygen. The difference of the absorbance of the sample before and after its pass through a cobalt oxide column was selected as analytical signal. As no further reagent was required this work can be considered as a contribution to environmental friendly analytical chemistry. The entire analytical procedure, including in-line sample dilution in three steps was automated by first, dilution in a stirred miniature vessel, second by dispersion and third by in-line addition of water using multisyringe flow injection technique. The dynamic concentration range was 0.04-0.78 gL(-1) (relative standard deviation lower than 3%), where the extension of the hypochlorite decomposition was of 90+/-4%. The proposed method was successfully applied to the analysis of commercial cleaning products. The accuracy of the method was established by iodometric titration.

A miniature and field­applicable multipumping flow analyzer for ammonium monitoring in seawater with fluorescence detection

In this article, a simple, economic, and miniature flow analyzer for ammonium in seawater based on the solenoid micropumps is presented. A single reagent of sodium tetraborate, ortho-phthaldialdehyde (OPA), and sodium sulfite was used and optimized applying the modified SIMPLEX method. A special-made detection cell for fluorescence detection of the reaction product isoindol-1-sulfonat was made and combined with a commercial photomultiplier tube, a long-pass optical filter, and an UV-LED as excitation light source. A LOD down to 13 nmol/L was achieved. The fabrication and application of a miniature reaction coil heating device for reaction rate enhancement is further described. The system featured an injection frequency of 32 h(-1) at average standard deviation of 3%.

Multisyringe flow injection analysis coupled to capillary electrophoresis (MSFIA–CE) as a novel analytical tool applied to the pre-concentration, separation and determination of nitrophenols

For the first time, a multisyringe flow injection analysis capillary electrophoresis system is described. The potential of the hyphenation for sample treatment including analyte pre-concentration is demonstrated by its successful application to the determination of mono-nitrophenols (NPs) in different water samples. The analytical system was used to automate in-line sample acidification, analyte pre-concentration, elution, hydrodynamic injection, electrophoretic separation, and detection as well as the maintenance and re-conditioning of the solid-phase extraction (SPE) column and the separation capillary. A pre-concentration factor of better than 115 and detection down to 0.11 micromol L(-1) were achieved. Detection was carried out at visible wavelength using a blue LED as a low baseline-noise light source. High repeatability was obtained each for migration times and for peak heights with relative standard deviations typically below 2.5 and 6% including the pre-concentration procedure, respectively. Three injections per hour were achieved by running in parallel the pre-concentrating and the electrophoretic separation procedures. Instrumental control and data registration and evaluation were carried out with the software package AutoAnalysis, allowing autonomous operation of the analytical system.

Development of a capillary electrophoresis system coupled to sequential injection analysis and evaluation by the analysis of nitrophenols

A combination of a laboratory-made capillary electrophoresis system and a sequential injection analysis equipment is described. For characterization, the system was successfully applied to the separation and quantification of nitrophenols. A blue LED was used as light source, and hydrodynamic injection was carried out by using a pressure-stable solenoid valve and an inflatable pressure reservoir. A good reproducibility of migration time (0.5%) and peak heights (5%) were obtained. The calibration by using peak heights was found to be linear up to 776 µmol L−1 for all three compounds. The system was robust and reliable for autonomous analysis without observation. All maintenance requirements including the conditioning of the capillary and flushing of both buffer reservoirs were carried out automatically. Instrumentation aspects of the capillary electrophoresis part are compared with former described hyphenated flow systems showing maximal operation versatility. Instrumental control and data evaluation were carried out using the software package AutoAnalysis.

Sequential injection analysis for automation of the Winkler methodology, with real-time SIMPLEX optimization and shipboard application

A multipurpose analyzer system based on sequential injection analysis (SIA) for the determination of dissolved oxygen (DO) in seawater is presented. Three operation modes were established and successfully applied onboard during a research cruise in the Southern ocean: 1st, in-line execution of the entire Winkler method including precipitation of manganese (II) hydroxide, fixation of DO, precipitate dissolution by confluent acidification, and spectrophotometric quantification of the generated iodine/tri-iodide (I(2)/I(3)(-)), 2nd, spectrophotometric quantification of I(2)/I(3)(-) in samples prepared according the classical Winkler protocol, and 3rd, accurate batch-wise titration of I(2)/I(3)(-) with thiosulfate using one syringe pump of the analyzer as automatic burette. In the first mode, the zone stacking principle was applied to achieve high dispersion of the reagent solutions in the sample zone. Spectrophotometric detection was done at the isobestic wavelength 466 nm of I(2)/I(3)(-). Highly reduced consumption of reagents and sample compared to the classical Winkler protocol, linear response up to 16 mg L(-1) DO, and an injection frequency of 30 per hour were achieved. It is noteworthy that for the offline protocol, sample metering and quantification with a potentiometric titrator lasts in general over 5 min without counting sample fixation, incubation, and glassware cleaning. The modified SIMPLEX methodology was used for the simultaneous optimization of four volumetric and two chemical variables. Vertex calculation and consequent application including in-line preparation of one reagent was carried out in real-time using the software AutoAnalysis. The analytical system featured high signal stability, robustness, and a repeatability of 3% RSD (1st mode) and 0.8% (2nd mode) during shipboard application.

Chip-On-Valve Concept: An Integrated Platform for Multisyringe Flow Injection Analysis: Application to Nitrite and Nitrate Determination in Seawater

A state-of-the-art flow lab-on-a-valve technique is reported incorporating integration of flow devices such as reaction and mixing serpentine coils and confluences into a monolith flow circuit mounted directly on an eight-port selection valve. The potential of the flow circuit manifold or chip-on-valve in combination with multisyringe flow injection analysis is demonstrated by the application to the successful determination of nitrite and nitrate in seawater. Characteristics and further potential of chip-on-valve are discussed. Due to preparation and fabrication by use of computer aided design, this chip design shows great potential for the automation of sophisticated flow networks in compact and robust flow circuits.

Sequential injection analyzer for glycerol monitoring in yeast cultivation medium

A smart and versatile flow system for the at-line monitoring of glycerol based on sequential injection analysis is proposed. Formaldehyde, generated by oxidation of glycerol with sodium periodate, is transformed into 2,4-diacetyl-1,4-dihydrolutidine applying the Hantzsch condensation reaction with acetylacetone and ammonium. Dual-wavelength detection was carried out to minimize the contribution of the schlieren effect using a single blue LED. In-line sample dilution is accomplished applying the concept of zone-penetration and a new concept of sample splitting. Under optimized physical and chemical variables, regression curves over two dynamic working ranges of 0.1-4 and 1-40g l(-1) were attained. The injection throughputs were 14 and 12h(-1), respectively. Applying on-line data evaluation and conditional inquiries, the smart and independent selection of the adequate analytical procedure for the required working range was accomplished. The system was successfully applied to the at-line monitoring of glycerol in a continuous, cell-free medium flow from a yeast cultivation process during batch and fed-batch phase with glycerol as the only carbon source.

Titanium determination by multisyringe flow injection analysis system and a liquid waveguide capillary cell in solid and liquid environmental samples

A multisyringe flow injection analysis system using a liquid waveguide capillary cell (MSFIA-LWCC) has been used for the spectrophotometric determination of titanium (Ti) in marine environmental samples. Samples were previous digested using potassium peroxodisulfate (K2S2O8). The method showed to be linear over a range up to 1 μM with a detection limit of 9.2 nM. The analysis consumes little reagent (250 μL) and sample (600 μL). It had an adequate accuracy with high repeatability (RSD of 1.8%) for all marine samples. The proposed method was used to evaluate the concentration of Ti in natural samples collected in the coastal area of the Majorca Island (Western Mediterranean Sea). We report average concentrations of Ti in coastal surface microlayer of 510.7 ± 267.2 nM, in surface sediments of 2.72 ± 1.84 μmol/g, and in rhizomes and leaves of Posidonia oceanica of 310 ± 295 nmol/g and 157 ± 132 nmol/g, respectively.

A multisyringe flow injection Winkler-based spectrophotometric analyzer for in-line monitoring of dissolved oxygen in seawater

An integrated analyzer based on the multisyringe flow injection analysis approach is proposed for the automated determination of dissolved oxygen in seawater. The entire Winkler method including precipitation of manganese(II) hydroxide, fixation of dissolved oxygen, dissolution of the oxidized manganese hydroxide precipitate, and generation of iodine and tri-iodide ion are in-line effected within the flow network. Spectrophotometric quantification of iodine and tri-iodide at the isosbestic wavelength of 466nm renders enhanced method reliability. The calibration function is linear up to 19mgL(-1) dissolved oxygen and an injection frequency of 17 per hour is achieved. The multisyringe system features a highly satisfying signal stability with repeatabilities of 2.2% RSD that make it suitable for continuous determination of dissolved oxygen in seawater. Compared to the manual starch-end-point titrimetric Winkler method and early reported automated systems, concentrations and consumption of reagents and sample are reduced up to hundredfold. The versatility of the multisyringe assembly was exploited in the implementation of an ancillary automatic batch-wise Winkler titrator using a single syringe of the module for accurate titration of the released iodine/tri-iodide with thiosulfate.