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.     

Chemometric studies in the Lagoon of Venice, Italy. Annual evolution of sulphur species and relationship to biogeochemical cycles in lagoon water

During the period March 1997-March 1998 dimethyl sulphide (DMS), dimethylsulphoniopropionate (DMSP) and carbon disulphide (CS2) were determined weekly in the water of the Lagoon of Venice, Italy (at three stations located in the Giudecca Canal, the San Secondo Canal and the Rio di San Nicolò). At the same time, the following hydrological and biological variables were also measured: tide height, temperature, transmittance, fluorescence, pH, salinity, chlorinity, sulphate, ammonia, nitrite, nitrate, phosphate, silicate, chlorophyll a, phaeopigments, phytoplankton (abundance and biomass). Principal component analysis (PCA), applied as a dimension reduction tool, made it possible to summarize multivariate information in a small number of components, which highlighted the relationships between the temporal evolutions of the sulphur compounds with hydrological and biological variables in the seasonal biogeochemical cycle of the lagoon. In particular the overall temporal cycle, which begins with the development of biological activity in late winter and spring, followed by the predominance of degradation processes during the late summer and the remineralization of nutrients in autumn, is clearly described in the plane of the first two principal components, together with the interrelationships between all the relevant variables.     

Temporal evolution of DMS and DMSP in Antarctic Coastal Sea water

The temporal evolution of concentrations of dimethylsulphide (DMS), its precursor dimethylsulphoniopropionate (DMSP) and chlorophyll a is surveyed weekly in the water column and in a landfast ice core at a coastal station of Gerlache Inlet (Terra Nova Bay, Antarctica) from 27 November 2000 to 14 February 2001. The DMS and DMSP profile concentrations in the water column are similar and show a clear temporal trend, with minimum values (<0.7?nM) at all depths occurring on 27 November 2000 and maximum values (4.8 × 10²?nM for DMS and 1.8 × 10²?nM for DMSP) in surface water on 27 December 2000 for DMS and on 19 December 2000 for DMSP. When the sea-ice cover is present, the temporal evolution of DMSP closely follows that of chlorophyll a in the water column, supporting the idea that DMSP, and therefore DMS, has a phytoplanktonic origin. However, when the ice cover breaks up during the late austral summer, a second phytoplankton bloom occurs, while the DMSP concentration in the sea-water column remains very low. In the ice core, the results show higher concentrations of DMSP than those of the underlying sea water, highlighting the important role of sea ice in the sulphur cycle of the Antarctic ecosystem.     

Sequential analysis of dimethyl sulfur compounds in seawater

A sequential method for the determination of dimethyl sulfur compounds, including dimethylsulfide （DMS）, dimethylsulfonio- propionate （DMSP） and dimethylsulfoxide （DMSO）, in seawater samples has been developed. Detection limit of 2.5 pmol of DMS in 25 mL sample, corresponding to 0.10 nmol/L, was achieved. Recoveries for dimethyl sulfur compounds were in the range of 68.6- 78.3%. The relative standard deviations （R.S.D.s） for DMS, DMSP and DMSO determination were 3.0, 5.4 and 7.4%, respectively.     

Determination of nitrite and nitrate in Venice lagoon water by ion interaction reversed-phase liquid chromatography

Ion interaction reversed-phase liquid chromatography with octylammonium orthophosphate as the interacting reagent and a reversed-phase C₁₈ column was applied to the identification and determination of nitrite and nitrate in Venice lagoon water. Interference by the high chloride concentration was systematically studied and the results obtained with different column packings were compared. With spectrophotometric detection at 230 nm, nitrite at 0.005 mg 1^?1 can be detected and determined even in the presence of 0.70 M chloride. The dependence of the retention time of nitrite on the chloride concentration was studied for two reversed-phase columns with different packings. Concentrations of 0.30 ± 0.05 mg 1^?1 of nitrite and 0.20 ± 0.05 mg 1^?1 of nitrate were found in Venice lagoon water.     

Benthic fluxes of trace metals in the lagoon of Venice

To assess the exchange and the mobility of trace metals between sediments and water and their geochemical behaviour, experiments were carried out within the sphere of the CORILA project for the safeguarding of the Venice lagoon. Trace element exchanges were examined for approximately 60 h at two sites in the central part of the Venice lagoon (Italy): the first one is located in front of the industrial area of Porto Marghera (Tresse) and the second one in front of Campalto, near the causeway (Campalto). The experiments were carried out using a benthic chamber monitored for pH, dissolved oxygen, salinity, and temperature. The temporal trend of metals inside the benthic chamber was examined in relation to changes of pH and dissolved oxygen. Diffusive metal fluxes were also assessed by determination of the vertical distribution of metals in pore water.Al, As, Cd, Cu, Fe, Mn, Mo, Sb, U, V and Zn were determined by ICP-SFMS. The metal concentrations for the lagoon samples were in agreement with expected values; the concentration ranges (min–max in ng/ml) were: Al 0.24–0.61, As 1.42–2.27, Cd 0.050–0.182, Cu 0.81–2.46, Fe 0.25–1.66, Mn 11.59–31.66, Mo 6.50–10.62, Sb 0.139–0.516, U 1.7–3.3, V 0.69–3.21, Zn 5.20–21.51.Positive fluxes for the Tresse and Campalto experiments were determined for Cd (0.21 and 0.18 pmol/cm²/h), Zn (62 and 67 pmol/cm²/h), Cu (0.29 and 0.50 pmol/cm²/h) and Mn (19 and 12 pmol/cm²/h), while negative fluxes were determined for iron (−3.5 and −6.3 pmol/cm²/h). Other elements showed differences in behaviour for the two experiments; the fluxes, for the Tresse and Campalto experiments, respectively, were 5.1 and −6.9 pmol/cm²/h for molybdenum, 0.25 and −0.18 pmol/cm²/h for arsenic and 1.3 and −8.4 pmol/cm²/h vanadium. Therefore, the different characteristics of the two areas affect the mobility of trace elements, which can derive from differences in the environmental characteristics of the two areas or seasonal difference in which the experiments were carried out.     

Environmental accounting for the lagoon of Venice and the case of fishing

This paper presents the application of the eMergy evaluation, introduced by H.T. Odum as an efficient methodology of environmental accounting. The results of this analysis are a part of a wider sustainability assessment for the Province of Venice realized in 2003. Within a territorial sustainability analysis, it is necessary to implement an environmental accounting method, which is able: to precisely consider the boundaries of the investigated system (spatial scale); to arbitrarily separate the life of the investigated system into periods (temporal scale); to account for both economic and natural support to a given territorial system in order to implement a sustainable management of resources; to assess all the items supporting the system on the basis of a physical unit that is objective (while the traditional economic evaluation method is based on individual preferences, hence it is subjective). The Province of Venice is a very complex system due, on one hand, to the heavy and consolidated presence of industrial activity since the beginning of the 20th century and, on the other hand, to the principal natural ecosystem which characterizes it: the lagoon, the largest wetland in the Mediterranean Sea. The role of the lagoon, as a provider of resources and services is represented by the analysis of two aspects: the lagoon as an ecosystem on the basis of the evaluation of all flows that cyclically support its biotic activity and the lagoon as a productive system on the basis of the contribution of both natural and "economic" inputs that support human activity. In particular, the case of clam fishing will be presented to put on evidence the importance of natural inputs that are systematically neglected by the traditional accounting methodologies.     

Quantitation of estrogens in ground water and swine lagoon samples using solid-phase extraction, pentafluorobenzyl/trimethylsilyl derivatizations and gas chromatography-negative ion chemical ionization tandem mass spectrometry

A method was developed for the confirmed identification and quantitation of 17beta-estradiol, estrone, 17alpha-ethynylestradiol and 16alpha-hydroxy-17beta-estradiol (estriol) in ground water and swine lagoon samples. Centrifuged and filtered samples were extracted using solid-phase extraction (SPE), and extracts were derivatized using pentafluorobenzy] bromide (PFBBR) and N-trimethylsilylimidazole (TMSI). Analysis was done using negative ion chemical ionization (NICI) gas chromatography-mass spectrometry-mass spectrometry (GC-MS-MS). Deuterated analogs of each of the estrogens were used as isotope dilution standards (IDS) and were added to the samples before extraction. A limit of quantitation of 1 ng/l in ground water was obtained using 500 ml of ground water sample, 1.0 ml of extract volume and the lowest calibration standard of 0.5 pg/microl. For a 25 ml swine lagoon sample, the limit of quantitation was 40 ng/l. The average recovery of the four estrogens spiked into 500 ml of distilled water and ground water samples (n = 16) at 2 ng/l was 103% (S.D. 14%). For 25 ml of swine lagoon samples spiked at 500, 1000 and 10,000 ng/l, the average recovery for the four estrogens was 103% (S.D. 15%). The method detection limits (MDLs) of the four estrogens spiked at 2 ng/l in a 500 ml of ground water sample ranged from 0.2 to 0.6 ng/l. In swine lagoon samples from three different types of swine operations, estrone was found at levels up to 25,000 ng/l, followed by estriol and estradiol up to levels at 10,000 and 3000 ng/l, respectively. It was found that pretreatment of swine lagoon samples with formaldehyde was necessary to prevent conversion of estradiol to estrone.     

Determination of natural and synthetic estrogenic compounds in coastal lagoon waters by HPLC-electrospray-mass spectrometry

A new analytical method was developed for the simultaneous determination of estrogenic compounds of natural (estradiol, estriol, estrone) and synthetic origin, both steroidal (ethinylestradiol, mestranol) and non-steroidal (benzophenone, bisphenol-A, diethylstilbestrol, octylphenol, nonylphenol, nonylphenol monoethoxylate carboxylate), in environmental aqueous samples by high-performance liquid chromatography coupled with ion trap-mass spectrometry via electrospray interface (HPLC-ESI-IT-MS). Quantitative MS detection was performed in the negative mode for all compounds except mestranol and benzophenone, which were detected under positive ion conditions. Very low method detection limits (MDLs), between 0.1 and 2.6?ng/L, were achieved in coastal lagoon water samples, while the developed solid-phase-extraction (SPE) procedure permitted simultaneous recovery of all analytes from spiked water samples with yields >70% (7–11 RSD%), except estriol and benzophenone, which were recovered with 60% (9 RSD%) and 50% (11 RSD%) yields, respectively. The proposed method was applied to the analysis of Venice (Italy) lagoon waters, where average concentrations of selected compounds in the 2.8–33?ng/L concentration range were found.     

Atmospheric input of organic pollutants to the Venice Lagoon

The atmospheric deposition of dioxins and furans (PCDD-Fs), dioxin-like polychlorobyphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs) and hexachlorobenzene (HCB) was determined in the Lagoon of Venice. Sampling was carried out monthly, for a total of 13 months (July 1998-July 1999) using "bulk" samplers (passive collectors of wet and dry depositions) at four sites, inside the lagoon and close to its edge. Calculated PCDD-F loadings to the Lagoon turned out to be quite homogeneous, their range being approximately 10-20 ng m-2 y-1, whereas in the station located close to the industrial zone of Porto Marghera the value was approximately 50 ng m-2 y-1. PCB deposition in the industrial fallout sampling site and in the city centre of Venice was approximately 2500 ng m-2 y-1, that is, almost five times higher than the values measured at the northern and southern lagoon stations. HCB annual loading (approximately 8000 ng m-2 y-1) was almost six times higher in the industrial zone than in the other sites (approximately 1500 ng m-2 y-1). PAH loadings in the city centre of Venice and at Porto Marghera were 314 and 389 micrograms m-2 y-1, respectively. The amount of 2,3,7,8-TCDD equivalents (TEQ) of PCDD-Fs and PCBs in the Venice and Porto Marghera bulk depositions was compared with the guideline value of 15 pg m-2 d-1 for dioxins in depositions proposed by De Fré et al. (1998). Moreover, as some of the effects which drive the risk assessment of dioxin-like compounds were also observed after exposure to other molecules, the TEQs of PAHs and HCB were also calculated: nine out of 13 samples exceeded the guideline value. Lastly, an atmospheric emission source related to vinyl chloride monomer production, which may affect atmospheric deposition on the whole Lagoon, is reported in the industrial zone of Porto Marghera.     

Sulfate determination in lagoon water (venice) by reversed-phase ion-interaction chromatography — a method validation

The validation of a new ion-interaction chromatographic method for sulfate determination is presented by the comparison with results obtained by ionchromatography. The two procedures were employed to quantify sulfate in model solutions and in samples of Venice lagoon water. The statistical t-test for multiple samples showed no significant difference between the two methods, at the 99% confidence level.     

Speciation of heavy metals in sediments of the lagoon of Venice collected in the industrial area

In this study a procedure of sequential extraction of metals from sediments was applied to samples from the lagoon of Venice. Compared to the measurement of total concentrations, the knowledge of metal partitioning among sediment phases can help in estimating the risk posed by metal polluted sediments and give information on contamination sources and on the factors that influence metal enrichment in sediments. The results permitted to estimate for each metal the percentage of the total content that could be potentially remobilized from sediments, owing to changes in environmental conditions. The immediately available fraction represented in general a low proportion of the total content. An important proportion of most metals (except for Zn, Cd and Cu) was associated to residual phases and therefore was not expected to be released under the normal environmental conditions. The large amounts of metals bound to Fe-Mn oxides/hydroxides confirmed the strong scavenging efficiency of this phase. The carbonate phase was the preferential associative form for Pb, Cd and Zn, whereas Cu was bound in prevalence to the organic matter/sulphide phase.     

Speciation analysis of mercury in seawater from the lagoon of Venice by on-line pre-concentration HPLC-ICP-MS

A method based on the coupling of HPLC with ICP-MS with an on-line pre-concentration micro-column has been developed for the analysis of inorganic and methyl mercury in the dissolved phase of natural waters. This method allows the rapid pre-concentration and matrix removal of interferences in complex matrices such as seawater with minimal sampling handling. Detection limits of 0.07 ng L(-1) for inorganic mercury and 0.02 ng L(-1) for methyl mercury have been achieved allowing the determination of inorganic mercury and methyl mercury in filtered seawater from the Venice lagoon. Good accuracy and reproducibility was demonstrated by the repeat analysis of the certified reference material BCR-579 coastal seawater. The developed HPLC separation was shown to be also suitable for the determination of methyl mercury in extracts of the particulate phase.     

A method to test the detectability of GC/PFPD for an extended concentration range with respect to reduced sulfur compounds

In this study, a possible means to extensively expand the quantifiable range of reduced sulfur compounds (RSC) in air has been investigated by a combined application of GC with pulsed flame photometric detector (PFPD) and a multifunction thermal desorber (TD) system. To comply with the purpose of this study, gaseous RSC standards containing the equimolar concentrations of H(2)S, CH(3)SH, DMS, DMDS, and CS(2 )were prepared at 11 concentration levels (i. e., 10 ppb-10 ppm (over 10(3 )range)). These standards were then used to derive three-point calibrations based on the modified injection through a TD (MITD). If the mean calibration slopes of each concentration level are normalized to that of CH(3)SH, the relative ordering is found as 0.65 (H(2)S): 1 (CH(3)SH): 1.34 (DMS): 2.24 (DMDS). The reproducibility of MITD method, when assessed in terms of relative standard error (RSE) for all calibration slopes, had the most stable pattern for DMDS (5.77%) and the least stable one for H(2)S (12.8%). The sensitivity of the MITD-based calibration generally improved with an increase in concentration levels of standard gas. Based on our study, the MITD technique is useful to extend quantification of GC/PFPD by allowing RSC detection over a 10(3) range.     

Fluoride accumulation in barnacles and mussels in the lagoon of Venice.

As some industries are likely to discharge fluoride into the Lagoon of Venice, especially in the area of Portomarghera, a survey was undertaken of the environmental levels of this element. Fluoride concentrations in the waters surrounding the industrial area ranged from 1.53 mg 1^?1 (chlorinity: 16.6‰) to 3.14 mg 1^?1 (15.1‰) and all values exceeded the levels considered normal for seawater having the same chlorinity.However determination of the fluoride content of water alone tells little about the entrance of this element into food chains. It therefore seemed appropriate to monitor the environment by examining organisms for their ability to accumulate fluoride in tissues. The organisms chosen for this purpose were the crustacean $\text{Balanus}$$\text{amphitrite}$ (barnacles) and the mollusk $\text{Mytilus galloprovincialis}$ (mussels). Both species were found to accumulate fluoride in their soft tissues to above-ambient levels. Maximum fluoride concentrations found for barnacles and mussels were 81 ± 6 μg g^?1 and 85 ± 20 μg g^?1 (dry weight) respectively; the concentration factor, calculated as the ratio of mean concentration of fluoride in dry soft tissue of the animal to mean concentration in water, was of the order of 10² for both species. Moreover seasonal variations in soft tissue fluoride concentrations were recorded. These seasonal variations are probably related to the reproductive cycle; in both species the highest fluoride levels were found during the spawning periods, that is in summer in the case of the barnacle and in winter and spring in the case of the mussel.These species, especially during their spawning periods, are indirectly or directly included in the human diet. Since fluoride can be toxic, more attention should be paid to levels in environments, like the Lagoon of Venice, in the vicinity of highly industrialized comunities in which a large amount of local seafood is included in the diet.     

Use of fluorescence spectroscopy and voltammetry for the analysis of metal-organic matter interactions in the New Caledonia lagoon

Fluorescence, polarographic and potentiometric analysis of sea water from the New Caledonia lagoon (located south of Noumea) allowed the determination of the specific properties of the dissolved and particulate phases of organic matter (OM)-metal complexes according to various regions of the lagoon. In particular, OM complexes with Ni, Zn, Pb, Cu, Cd were chosen in this study due to the sensitivity of these complexes to affect biocenosis of the nearby enclosed coral reef as well as their availability to enter the coast from erosion (terrigenous OM) or human activities from nickel extraction or pollution from waste sites (anthopogenic OM) that exist throughout New Caledonia. Combined with geochemical modelling, the OM-metal complexes analysis allowed the determination of their conditional stability constants which in turn helped in predicting the fate of the metal pollution in the lagoon. For the first time, fluorescence, polarographic and potentiometric techniques combined with geochemical models that employed discrete pKa distribution on OM enabled the determination of the origin of the OM, as either natural or anthopogenic.     

Determination of plutonium radioactivity in Mururoa lagoon water

This study presents the plutonium radioactivity levels measured in Mururoa lagoon water during the 1985–1991 period.The low radioactivity levels recorded, from 10^–2 to 1.5 Bq/m³ are due to the slow solubilization of plutonium deposited in lagoon sediments following atmospheric experiments which took place from 1966 to 1974. The average concentrations of the lagoon water tend to decrease from one year to the next. However, the influence of the weather conditions is discussed.The Mururoa lagoon being open to the ocean, plutonium radioactivity traces are still detectable in the immediate vicinity of the atoll.     

Core level (S 2p) excitation and fragmentation of the dimethyl sulfide and dimethyldisulfide molecules

Electronic excitation and ionic dissociation of dimethylsulfide (DMS) and dimethyldisulfide (DMDS) have been studied around the S 2p edge using synchrotron radiation and time-of-flight mass spectrometry techniques. Mass spectra were obtained for both molecules, below, on and above the well defined resonances observed in the S 2p photoabsorption spectrum and centered at approximately 166 eV photon energy. Ab initio IS-CASSCF calculations were performed for a better understanding of the photoabsorption spectra. Similar calculations were also performed for the H(2)S molecule, in order to establish a bench mark. For both molecules, a higher fragmentation degree is observed with increasing photon energy. In the DMDS case, selective fragmentation was observed in the formation of the [CH(n)S](+) ions at the first S 2p resonance (corresponding to excitation to a σ*SS state) and in the formation of the [S(2)](+) and [S](+) ions at the third S 2p resonance (corresponding to excitation to a σ*CS state). Previously unreported doubly charged ([S](2+), [CH(3)](2+)) are observed for DMS and DMDS.     

Resonance Rayleigh scattering for the determination of cationic surfactants with Eosin Y

Resonance Rayleigh scattering (RRS) of cationic surfactants–Eosin Y systems and their analytical application have been studied. In aqueous solution at pH 2∼3, Eosin Y reacts with a monomer of cationic surfactants (CS), such as Zephiramine (Zeph), tetradecylpyridinium bromide (TPB), cetylpyridinium bromide (CPB), cetylpyridinium chloride (CPC) and cetyltrimethylammonium bromide (CTMAB), to form an ion associate and a new RRS spectrum appears. The spectral characteristics of the five ion associates are similar and their maximum scattering wavelengths (λ_max) are all at 313 nm. The intensity of RRS at λ_max of the ion associate is directly proportional to the concentration of CS in the range of 0∼3.0 μg/25 mL. The technique has high sensitivity for the determination of CS; their detection limit is between 5.57 ng/mL and 7.60 ng/mL depending on the CS. In this case, most metal and non-metal ions, NH₄ ⁺ and some anionic surfactants do not interfere, so that the method has a good selectivity. It can be applied to the determination of trace amounts of cationic surfactants in water samples. Received: 9 September 1998 / Revised: 17 November 1998 / Accepted: 18 November 1998     

Does a high UV environment ensure adequate vitamin D status?

This study assesses the Vitamin D status of 126 healthy free-living adults aged 18-87 years, in southeast Queensland, Australia (27 degrees S) at the end of the 2006 winter. Participants provided blood samples for analysis of 25(OH)D (the measure of an individual's Vitamin D status), PTH, Calcium, Phosphate, and Albumin, completed a questionnaire on sun-protective/sun-exposure behaviours, and were assessed for phenotypic characteristics such as skin/hair/eye colour and BMI. We found that 10.2% of the participants had serum 25(OH)D levels below 25 nmol/l (considered deficient) and a further 32.3% had levels between 25 nmol/l and 50 nmol/l (considered insufficient). Our results show that low levels of 25(OH)D can occur in a substantial proportion of the population at the end of winter, even in a sunny climate. 25(OH)D levels were higher amongst those who spent more time in the sun and lower among obese participants (BMI>30) than those who were not obese (BMI<30). 25(OH)D levels were also lower in participants who had black hair, dark/olive skin, or brown eyes, when compared with participants who had brown or fair hair, fair skin, or blue/green eyes. No associations were found between 25(OH)D status and age, gender, smoking status, or the use of sunscreen.