Winter evolution of DMS and DMSP in Venice lagoon water and sediment

The evolution of dimethylsulphide (DMS) and dimethylsulphoniopropionate (DMSP) concentrations in the water and sediment of the Venice lagoon were studied together with the concentration of chlorophyll a, temperature and the composition and density of phytoplankton to understand the role of the sediment as a source of DMS during the winter period. The temporal trend of water DMS concentration in this period showed a maximum concentration in February (75.7 nmol S l-1) related to low DMSP and chlorophyll a concentrations but to high phytoplanktonic abundance. The DMS and DMSP concentrations were greater in the sediment than in the water. The temporal trend of DMS concentration in sediment showed a maximum in February (1155 nmol S l-1) related to the maximum of DMS concentration in surface water. These observations suggested that in the winter period DMS could be produced by the conversion of the DMSP present in the bulk water but principally by that present in the sediment (microbiological degradation of DMSP or other sulphur-containing compounds) that subsequently diffuse in water.     

Study of organic sulphur compounds (DMS,DMSP and CS2) in lagoon ecosystems: the case of the Venice lagoon

This study of the origin and fate of dimethyl sulphide (DMS) in a particular and complex lagoon ecosystem such as that of the Venice lagoon focuses on the temporal evolutions of DMS concentrations in surface water together with those of dimethylsulphoniopropionate (DMSP), carbon disulphide (CS2), nutrients (nitrate, nitrite, ammonium, phosphate, silicate), sulphate, chlorophyll a, chlorinity, water temperature and phytoplankton (composition and density). Measurements were made from 3 March 1997 to 23 July 1998 at three stations in the central part of the Venice lagoon. The temporal trends of DMS concentration showed an absolute maximum concentration in winter (65 nmol S/l, 19/2/1998, Stn. 1; 119 nmol S/l, 19/2/1998, Stn. 2; 29 nmol S/l, 17/2/1998, Stn. 3) and two relative maxima in the spring-summer period. The spring-summer secondary maxima of DMS concentration were related to the maxima of DMSP and chlorophyll a concentrations and consequently to phytoplanktonic abundance while the winter DMS maximum showed no relation to DMSP or to chlorophyll a suggesting that the production and the fate of DMS could be different for the two periods. According to previous studies the CS2 concentration increased in the spring, achieved its maximum in summer, decreased in autumn and fell to its minimum in winter.     

Ultraviolet Radiation in a High Mountain Lake of the Austrian Alps: Air and Underwater Measurements

Global UV radiation was measured with a portable multichannel filter radiometer at the surface and underwater in a high mountain lake (2417 m above sea level) of the Austrian Alps during 16 days in summer 1995. During this period, total column ozone values that changed only by 34 Dobson units explained a significant part of the variability in UVB radiation at 305 nm as indicated by the negative correlation with the ratio 305:340 nm (r_s= -0.810, P < 0.01). High radiation at the surface combined with high water transparency allowed substantial UVB radiation to reach the bottom of this lake. The diffuse attenuation coefficient for downward irradiance at 305 nm changed within 2 weeks from 0.24 m^-1 (10% at 9.6 m depth) to 0.32 m^-1 (10% at 7.2 m depth). This change in attenuation was related to the development of phytoplankton after the ice break-up as indicated by a six-fold increase in chlorophyll-a concentrations during this period. Our results suggest that phytoplankton and/ or phytoplankton-derived organic substances are important for the UV attenuation in this oligotrophic lake.     

Development of an efficient method for the preparative isolation and purification of chlorophyll a from a marine dinoflagellate Amphidinium carterae by high-speed counter-current chromatography coupled with reversed-phase high-performance liquid chromatography

In our research into chlorophylls of marine dinoflagellates, chlorophyll a was separated rapidly from the hexane extract of Amphidinium carterae in three steps. The first step was silica gel column chromatography, where elution was performed with 0–50% ethyl acetate in n-hexane. The second was high-speed counter-current chromatography using a two-phase solvent system consisting of n-hexane–ethyl acetate–methanol–water (5:5:5:1, v/v), and the third step was preparative reversed-phase high-performance liquid chromatography using a solvent system of acetone–water (89:11, v/v). HPLC analysis showed that the purity of chlorophyll a from the second step was over 83%, and after the third it was over 99%. Thirty milligrams of chlorophyll a was isolated from a crude sample of 250 mg of chlorophylls, and its structure was identified by analyzing its MS, ¹H NMR and ¹³C NMR spectra.     

Off-line separation and determination of rare earth elements associated with chloroplast pigments of hyperaccumulator Dicranopteris dichotoma by normal-phase liquid chromatography and ICP–MS

An off-line normal-phase liquid chromatography–ICP–MS method has been used for separation and determination of the rare earth elements (REE) associated with chloroplast pigments of Dicranopteris dichotoma. The stability of REE-bound pigments was tested, and almost no destruction of REE-bound pigments occurred during the so-called normal-phase liquid chromatography. The accumulated free REE ions on the microcrystalline cellulose column were cleaned by elution with 5 mmol L^–1 2-ethylhexyl hydrogen 2-ethylhexylphosphonate (P507), to avoid exchange of these free ions with metals from the pigments. When these precautions were taken, the method was applied to the study of REE-bound pigments in D. dichotoma. ICP–MS results showed REE were present in chlorophylls and lutein, although REE concentrations in carotene and pheophytin were both below procedural blank levels. By careful analysis of the eluate fractions containing chlorophyll a it was found that REE-bound chlorophyll a in D. dichotoma was slightly enriched in the fractions with relatively short retention time. Results indicated that the retention time of REE-bound chlorophyll a might be slightly less than that of magnesium chlorophyll a, and REE-bound chlorophylls might be of relatively low polarity in comparison with magnesium bound chlorophylls. This phenomenon could be explained by the special double-decker sandwich-structure of REE-bound chlorophylls, as was reported by us and other authors. On the basis of these results we preferred to consider that REE can replace magnesium in chlorophyll a of D. dichotoma, and that the role of REE-bound chlorophylls in photosynthesis cannot be neglected. These data might be useful for understanding of both the properties of REE-bound pigments and the effect of REE on plant photosynthesis.     

FAR-INFRARED SPECTRA OF LANGMUIR-BLODGETT FILMS OF CHLOROPHYLL a,CHLOROPHYLL b,PHEOPHYTIN a and THEIR ADDUCTS WITH WATER and DIOXANE*

Fourier transform infrared spectra in the low frequency region (500–150cm^?1) of Langmuir-Blodgett films of chlorophyll a (Chi a), chlorophyll b (Chi b) and pheophytin a have been studied. Correlations between spectral changes in monolayer and multilayers of Chi a and Chi b and their adducts with water and dioxane have been established. Spectroscopic evidence has indicated that, although there are no individual absorption bands that can be assigned to pure Mg-nitrogen and/or Mg-oxygen stretching or bending modes, there are several bands in the400–200 cm^?1 region of the spectra containing considerable contributions from metal-nitrogen and metal-oxygen vibrational modes. These specific vibrations exhibit marked intensity changes and shifts upon water and dioxane interaction. The different states of chlorophyll aggregation in Langmuir-Blodgett mono- and multilayers films resulted in noticeable changes in their far-IR spectra.     

An in-tube SPME device for the selective determination of chlorophyll a in aquatic systems

We report a new device for the estimation of the content of chlorophyll a pigment in water samples as an indicator of water quality. The extraction of the pigment from water was also optimized. 10 mL of water was filtered through a nylon filter (45 μm pore size and 13 mm of diameter), after the chlorophylls were dissolved by immersing the filter in 1 mL of a low non-hazardous solvent as ethanol. An in-valve in-tube SPME device coupled to capillary liquid chromatography with diode array detection was designed. A capillary column of 70 cm in length (0.32 mm i.d. coated with 5% diphenyl-95% polydimethylsiloxane, 3 μm coating thickness) was used as the loop of the injection valve for preconcentration and a Zorbax SB C₁₈ (SiO₂-based) 150 mm × 0.5 mm i.d., 5 μm column (Agilent) was used as analytical column. The achieved detection limit was 0.05 μg L⁻¹ and the working range of concentrations was 0.1-1 μg L⁻¹. % RSD values between 2 and 11 were obtained. Chlorophyll a in several water matrices was determined with good results in presence of other pigments such as chlorophyll b, pheophytin a and pheophytin b.     

EXCITATION TRANSFER BY CHLOROPHYLL a IN MONOLAYERS AND THE INTERACTION WITH CHLOROPLAST GLYCOLIPIDS*

In mixed monolayers with purified chloroplast glycolipids and other colorless lipids, chlorophyll a fluorescence exhibits a decrease in quantum efficiency with increasing chlorophyll concentration. The fluorescence, which is strongly polarized in dilute films, becomes progressively depolarized as the area fraction of chlorophyll increases, and it is completely depolarized in a pure chlorophyll a monolayer. The observed behavior is consistent with an inductive resonance mechanism of energy transfer among the chlorophyll molecules with a critical transfer distance of 20–90 Å, depending on the model chosen for the energy transfer mechanism. The purified glycolipids–mono-and digalactosyl diglycerides and sulfoquinovodiglyceride–separately form stable, compressible monolayers of the liquid-expanded type on an aqueous subphase and in an atompshere of nitrogen. At maximum compression the three glycolipids occupy areas of 55, 80 and 47 A²-molecule^-1, respectively, in the monolayer. Mixed monolayers of chlorophyll a with, separately, the monogalactolipid and the sulfolipid behave upon compression as two-dimensional solutions. The fluorescence polarization at high chlorophyll concentrations in mixed monolayers indicates that several of the lipid diluents facilitate local ordering of the pigment molecules.     

Epoxidation of (Z)-3-Arylidene-1-thioflavanones

Summary.  Epoxidation of (Z)-3-arylidene-1-thioflavanones by sodium hypochlorite or alkaline hydrogen peroxide afforded diastereomeric mixtures of trans,cis- and trans,trans-epoxides. These were separated by silica gel column chromatography. Determination of the isomeric composition of the crude reaction products and structure elucidation of all new isolated epoxides were performed by ¹H and ¹³C NMR spectroscopy. Received November 10, 2000. Accepted December 19, 2000     

Applicability of micellar electrokinetic chromatography to the analysis of estrogens in water

Estrone, β-estradiol and ethynylestradiol spiked in water were extracted using solid-phase extraction (SPE) and then directly determined by micellar electrokinetic chromatography (MEKC) with online concentration (sweeping). A 350 mL original sample volume (10 nM each) was concentrated to 1 mL using SPE, and ca. 240 nL of this solution was injected onto an MEKC capillary column. After sweeping, the estrogen related compounds were detected using a commercial absorbance detection system with an LOD of 0.16–0.30 nM in the original sample. Received: 15 September 2000 / Revised: 16 November 2000 / Accepted: 20 November 2000     

A microprocessor-controlled,multichannel fluorimeter for analysis of sea water

The multichannel fluorimeter described provides good sensitivity and rapid data acquisition. The advantages of multichannel fluorescence detection are discussed with special reference to the continuous monitoring of in vivo chlorophyll fluorescence in sea waters. Experiments on chlorophyll a determinations indicate a detection limit of 5 × 10^?12 M with a linear range over at least three orders of magnitudes of concentration.     

Stereochemical Course of the Formation of the C(7)‐Formyl Group from a Chiral Methyl Group during the Transformation of Chlorophyllide a into Chlorophyllide b

The biosynthesis of chlorophyll a and chlorophyll b from (2R,3R)‐ and (2S,3S)‐5‐amino[2,3‐¹⁴C₂,2,3‐²H₂,2,3‐³H₂]levulinic acid in greening barley has established that chlorophyllide a oxidase catalyses the transformation of the methyl group at C(7) of chlorophyllide a into the CHO group of chlorophyllide b with the loss of H^Si from the 7‐(hydroxymethyl)chlorophyllide intermediate.     

High performance liquid chromatographic separation of polar and non-polar chlorophyll pigments from algae using a wide pore polymeric octadecylsilica column

A method employing a wide pore polymeric reversed phase column has been developed for the separation of most of the chlorophylls and related compounds previously described as occurring in marine microalgae. The high selectivity toward molecular shape of this kind of stationary phase has enabled compounds of very similar structure, such as chlorophylls c₁, c₂ and Mg-divinylpheoporphyrin a₅ monomethyl ester, and chlorophyll a and the phytol-substituted chlorophyll c-like pigments, which commonly coelute on monomeric bonded phases, to be resolved in a single run. Some of these pigments, formerly thought to be a single compound, have, in fact, been demonstrated to be groups of two or more. The method has been successfully applied to both algal cultures and natural sea water samples. When visible light absorbance detection was used, the method proved suitable for separation of various carotenoids.     

Basicity of some aliphatic amines in mixed H2O?CH3CN solvents

The values of pK_a^ms (K_a^ms represents ionization constant of conjugate acid of amine base in mixed water–acetonitrile solvent) for all amines, except for charged amine bases, show a mild decrease (ca. 0.1–0.4 pK units) with the increase in CH₃CN content from 2 to ∼60% v/v. However, the pK_a^ms values at 70% v/v CH₃CN become nearly equal or slightly larger (by ≤0.7 pK units) than the corresponding pK_a^ms at 2% v/v CH₃CN for all neutral and charged amines. The values of pK_a^ms for phenol increase from 10.17 to 13.38 with the increase in the content of CH₃CN from 2 to 70% v/v in mixed aqueous solvent. Taft reaction constants, ρ*, obtained from the plots of pK_a^ms against ∑σ* for primary and secondary amines decrease by ca. 0.8 ρ* units with the increase in the CH₃CN content from 2 to 70% v/v. The values of pK_a^ms show an empirical linear relationship with the corresponding values of pK_a^w (where pK_a^w represents the pK_a obtained in aqueous solvent containing 2% v/v CH₃CN), which allows the estimation of a pK_a in mixed H₂O CH₃CN solvents from that in water. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 146–152, 2000     

On the photodecomposition of chlorophyll in vitro. I. Reaction rates

Abstract— Chlorophyll solutions are irreversibly bleached by light in the presence of oxygen. The action spectra parallel the absorption spectra for both chlorophyll a and b. The reaction is of second order with a Q₁₀ of 1.26. The reaction rates for chlorophylls a and b are of the same order of magnitude. Depending upon the light source, the initial rate for chlorophyll a is slightly higher, by a factor of 1.15 to 1.30. The rate for pheophytin is lowe 3 by several orders of magnitude. No pheophytin has been detected in the reaction products of the irradiated chlorophyll solutions in the absence of water.     

Ultra low level deep water <Superscript>137</Superscript>Cs activity in the South Pacific Ocean

We determined ¹³⁷Cs concentrations in deep water samples of the subtropical gyre in the South Pacific collected during the BEAGLE2003 cruise. This was done at an underground facility to achieve extremely low background γ-spectrometry, and we, therefore, obtained reliable values of ¹³⁷Cs activity in the deeper layers. ¹³⁷Cs activity in the layers between 2000 and 4500 m ranged from 7 ± 4 mBq m⁻³ to 25 ± 11 mBq m⁻³. The inventory of ¹³⁷Cs in the water column from 2000 m to the sea bottom was estimated to be 20 ± 8 Bq m⁻² to 94 ± 41 Bq m⁻² in this region.     

Development of a sampling and flow injection analysis technique for iron determination in the sea ice environment

A trace metal clean method for sampling and analysis of iron is set up and applied to sea ice and its associated snow, brine, and underlying seawater sampled during the Antarctic expedition “ARISE in the East” (Antarctic Remote Ice Sensing Experiment, AA03-V1, September-October 2003, 64-65°S/112-119°E, RV Aurora Australis). For clean sampling, a non-contaminating electropolished stainless steel ice corer is designed in conjunction with a polyethylene lathe equipped with Ti chisels to remove possibly contaminated outer layers of ice cores. A portable peristaltic pump with clean tubing is used on the ice to sample the underlying seawater (interface ice-water = 0, 1 and 30 m) and sea ice brine from access holes. Considering the extreme range of salinities (1-100) and Fe concentrations (0.1-100 nM) previously observed in similar environments, it is of paramount importance to set up a simple and sensitive Fe analyser adapted to such gradients. We use a flow injection analysis (FIA) technique and successfully demonstrate its capability to measure Fe concentrations directly in the sample without an on-line preconcentration/matrix separation step. We test the sensitivity, accuracy, precision and long-term stability of the analytical procedure. Also we explore and remediate interferences from a suite of other trace elements, such as Ni, Cd, Cr, Mn, Cu, Zn and Co. Analysis of reference materials NASS-5 and CASS-3 gives a good agreement with the certified values. Repeated measurements over a period of 5 months of an “in-house” Antarctic seawater standard yields a concentration of 1.02 ± 0.07 nM (n = 17, 1σ). The detection limit (3σ of the blank) is on average 0.12 nM. We report here results of the Fe distribution in sea ice that are in good agreement with previously published data. To our knowledge, this work provides the first complete profiles of total dissolvable and dissolved Fe in sea ice.     

The Distribution of Arsenic Compounds in the Ocean: Biological Activity in the Surface Zone and Removal Processes in the Deep Zone

The vertical profies of inorganic arsenic [As(III)+As(V)], monomethylarsonic acid (MMAA) and dimethylarsinic acid (DMAA) were investigated at four sampling stations in the Pacific Ocean and a sampling station in the southern Tasman Sea. In addition, the concentrations of those compounds in surface waters of the Pacific Ocean and Tasman Sea have been determined. The vertical profiles of inorganic arsenic showed the low concentrations in both the surface and deep/bottom zones. The depleted concentrations in the surface zone varied from 1000 to 1700 ng dm⁻³ and that in the deep/bottom zone varied from 1300 to 2050 ng dm⁻³. The maximum concentrations that varied from 1500 to 2450 ng dm⁻³ were usually observed at a depth of about 2000 m. Both MMAA and DMAA were observed throughout the water column at sampling stations in the north-western and equatorial regions of the Pacific Ocean. At the sampling station in the central northern Pacific gyre, DMAA was the only methylated arsenic compound observed throughout the water column. On the contrary, at the sampling station in the southern Tasman Sea, the only detected methylated arsenic compound throughout the water column was MMAA. Their vertical profiles showed maximum concentrations in the surface water which abruptly dropped with depth from 0 to 200 m. The concentration in the surface water was close to 10 ng dm⁻³ for MMAA and varied from 27 to 185 ng dm⁻³ for DMAA. At depths greater than 100 m, MMAA and DMAA were at comparable concentrations which varied from 0.7 to 14 ng dm⁻³. The low inorganic arsenic concentration in the surface zone was due to biological activity. This activity resulted in the uptake of As(V) and subsequent reduction and methylation to MMAA and DMAA. DMAA was the main predominant arsenic compound resulting from biological activity in surface waters. The low inorganic arsenic concentrations in the deep and bottom zones were likely to be caused by the adsorption of dissolved inorganic arsenic onto sinking particulates rich in iron and manganese oxides.     

Mechanisms and parameters of transients and oscillations of delayed chlorophyll fluorescence in the thylakoid membrane of the intact maize leaf

Standard induction processes of delayed fluorescence (DF) of chlorophyll (induction signals) occur when an intact leaf segment of maize inbreds and hybrids is initially kept in the phosphoroscope darkroom for more than 15 min (τ > 15 min), and then the leaf is illuminated with the intermittent white light and measured. Resolved induction processes of DF chlorophyll into transients: A, B, C, D, and E occur when the intact leaf segment of maize inbreds and hybrids is kept in the phosphoroscope darkroom for a significantly shorter period (30 s ≤ τ ≤ 240 s), with the time rate τ of 30 s, prior to its illumination with the intermittent white light. Induction transients: A, B, C, D, and E are characterised with their temporal parameters: t _A, t _B, t _C, t _D, and t _E, dynamics of changes in transients intensities and mechanisms of their generation. The induction processes of chlorophyll DF of the intact leaf of maize inbreds and hybrids resolved into transients: A, B, C, D, and E are accompanied by the occurrence and different levels of activation energy (E _a, kJ mol⁻¹) that correspond to different critical temperatures. The generation mechanisms of induction transients: A, B, C, D, and E are classified into two groups. Transients A and B are of a physical character, while the transients: C, D, and E are of a chemical character. It is shown that the generation of the induction transients: B, C, D, and E simultaneously follows establishing of the oscillations of induction processes of the DF chlorophyll. Oscillating of induction processes of DF chlorophyll is explained by the ion (K⁺, Na⁺, H⁺, Cl⁻) transport mechanism across the thylakoid membrane of the intact leaf of maize inbreds and hybrids grown under conditions of air drought, increased temperatures and water deficiency in the medium. The article is published in the original.     

Seasonal Impacts of Solar UV Radiation on Photosynthesis of Phytoplankton Assemblages in the Coastal Waters of the South China Sea

We carried out experiments to evaluate seasonal changes in the impacts of UV radiation (UVR, 280–400 nm) on photosynthetic carbon fixation of phytoplankton assemblages. Surface water samples were obtained in the coastal area of the South China Sea, where chlorophyll a ranged 0.72–3.82 μg L⁻¹. Assimilation numbers (photosynthetic carbon fixation rate per chl a) were significantly higher during summer 2005 than those in spring and winter 2004. The mean values obtained under photosynthetically active radiation (PAR) were 2.83 (spring 2004), 4.35 (winter 2004) and 7.29 μg C (μg chl a)⁻¹ h⁻¹ (summer 2005), respectively. The assimilation numbers under PAR + UVR were 1.58, 2.71 and 5.28 μg C (μg chl a)⁻¹ h⁻¹, for spring, winter and summer, respectively. UVR induced less inhibition of photosynthesis during summer 2005 than during the other seasons, in spite of the higher UVR during summer. The seasonal differences in the productivity and photosynthetic response to UV were mainly due to changes in water temperature, while irradiance and vertical mixing explained >80% of the observed variability. Our data suggest that previous studies in the SCS using UV-opaque vessels might have overestimated the phytoplankton production by about 80% in spring, 61% in winter and 38% in summer.