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1.
The role of the major biogeochemical processes in Hg cycling at the sediment–water interface was investigated in the Grado Lagoon (Northern Adriatic Sea). This wetland system has been extensively contaminated from the Idrija Hg Mine (Slovenia) through the Isonzo River suspended load carried by tidal fluxes. Three approaches were used to study the sediment–water exchange of total Hg (THg), methylmercury (MeHg), reactive Hg (RHg) and dissolved gaseous Hg (DGHg): (1) estimation of diffusive fluxes from porewater and overlying water concentrations, (2) measurements of benthic fluxes using a deployed light benthic chamber in situ and (3) measurements of benthic fluxes during oxic–anoxic transition with a laboratory incubation experiment. The THg solid phase, ranging between 9.5 and 14.4 μg g−1, showed slight variability with depth and time. Conversely, MeHg contents were highest (up to 21.9 ng g−1) at the surface; they tended to decrease to nearly zero concentration with depth, thus suggesting that MeHg production and accumulation occur predominantly just below the sediment–water interface. Porewater MeHg concentrations (0.9–7.9 ng L−1, 0.15–15% of THg) varied seasonally; higher contents were observed in the warmer period. The MeHg diffusive fluxes (up to 17 ng m−2 day−1) were similar to those in the nearby Gulf of Trieste [Covelli, S., Horvat, M., Faganeli, J., Brambati, A., 1999. Porewater distribution and benthic flux of mercury and methylmercury in the Gulf of Trieste (Northern Adriatic Sea). Estuar. Coast. Shelf Sci. 48, 415–428], although the lagoon sediments contained four-fold higher THg concentrations. Conversely, the THg diffusive fluxes in the lagoon (up to 110 ng m−2 day−1) were one- to two-fold higher than those previously estimated for the Gulf of Trieste. The diurnal MeHg benthic fluxes were highest in summer at both sites (41,000 and 33,000 ng m−2 day−1 at the fishfarm and in the open lagoon, respectively), thus indicating the influence of temperature on microbial processes. The diurnal variations of dissolved THg and especially MeHg were positively correlated with O2 and inversely with DIC, suggesting an important influence of benthic photosynthetic activities on lagoon benthic Hg cycling, possibly through the production of organic matter promptly available for methylation. The results from the dark chamber incubated in the laboratory showed that the regeneration of dissolved THg was slightly affected by the oxic–anoxic transition. Conversely, the benthic flux of MeHg was up to 15-fold higher in sediments overlain by O2 depleted waters. In the anoxic phase, the MeHg fluxes proceeded in parallel with Fe fluxes and the methylated form reached approximately 100% of dissolved THg. The MeHg is mostly released into overlying water (mean recycling efficiency of 89%) until the occurrence of sulphide inhibition, due to scavenging of the available Hg substrate for methylation. The results suggest that sediments in the Grado Lagoon, especially during anoxic events, should be considered as a primary source of MeHg for the water column.  相似文献   
2.
The aqueous photochemical transformation of acrylic acid   总被引:3,自引:0,他引:3  
Acrylic acid in sea water is thought to occur mostly as the product of microbial cleavage of dimethylsulphoniopropionate (DMSP), but could also be a pollutant introduced by waste waters of the organic chemical industry. Solutions of acrylic acid in natural and artificial sea water, and distilled and riverine water were photolyzed using a photochemical reactor and exposure to sunlight. The transformation of acrylic acid comprises the decarboxylation of the carboxylic group and subsequent polymerization to a polyethylene type molecule. Kinetic studies showed the lowest reaction rate in distilled water and somewhat higher and very similar rates in other aqueous media. The approximately similar reaction rates in all natural waters studied suggest that inorganic ions, especially Na+, Mg2+ and halides, and dissolved organic matter (probably humics) enhance the reaction rates. On studying the influence of different concentration ranges on the reaction kinetics, an exponential increase of rates with decreasing concentration was found. The reaction rate in the sea water solution in field conditions is rather slow. In thirty days exposure about 15% of the reactant was transformed. This reaction seems to be important in the marine environment in specific conditions, especially in phycospheres and macroaggregates where higher concentrations of acrylic acid inhibit the bacterial metabolism.  相似文献   
3.
Abstract. Benthic fluxes of dissolved N. Si and P nutrients, alkalinity, dissolved inorganic C (DIC), and O2 from sediments in the Gulf of Trieste (northern Adriatic, Italy) were measured monthly for 16 months, using laboratory incubated flux chambers at in siru temperatures in the dark. The annual average fluxes were: 02 = -19.3 ± 8.2, DIC = 13.7 ± 9.6, NO3 = -0.04 ± 0.16, NH4 = 0.3 ± 0.4. PO4= 4.001 ± 0.01, Si = 0.9 ± 0.1 mmol m-2 d-1, with strong temporal fluctuations. The highest effluxes of all nutrients and DIC were observed in the summer. Small effluxes of DIC and NH4 and influxes of Si and PO4 were observed in late winter. Only NH4 (ca. 50%) and Si (ca. 70%) fluxes were significantly correlated with temperature. This correlation suggests that the rate of downward input and the quality of sedimented organic matter (autochthonous and allochthonous) were superimposed on the temperature fluctuations. High DIC, NH4 and Si effluxes observed in May 1993 during low temperature were due to the degradation of sedimentary organic matter produced by an early spring bloom of benthic microalgae which occurred about 6 weeks earlies while the autumn phytoplankton bloom was simultaneously reflected in enhanced benthic fluxes due to higher temperature. The role of benthic biological advection in this transport across the sediment-water interface, evaluated by comparison between measured benthic and calculated diffusive fluxes from nutrient pore water concentrations, was of minor importance. This is probably due to low infaunal activity throughout the year it was localized mostly in the narrow surficial layer. The annual average diffusive fluxes of NH4 and PO4 were higher than those measured, probably due to the presence of nitrificationdenitrifi-cation processes and redox-dependent chemical reactions at the oxic sediment-water interface, respectively. Only during bottom-water hypoxia in September 1993 did strong PO4 effluxes prevail. Calculations based on the Redfield stoichiometry of oxic decomposition of organic N to NH4 and NO3, and differences between diffusive and measured NH4 fluxes showed that denitrifkation averaged 0.8 mmol m-2 d-1. Significant correlations between NH4 and PO4 DIC and Si, and NH4 and Si fluxes suggested their parallel regeneration and utilization at the sediment-water interface. The nutrient fluxes observed were not significantly linked to O2 consumption, suggesting also that anaerobic oxidation processes were important at the sediment-water interface in the gulf. The N, P and Si nutriqnts released from sediment pore waters are probably utilized in benthic microalgal and bottorn-hater primary production. This indicates that pelagic and benthic communities in the central part of the Gulf of Trieste function relatively independently of each other.  相似文献   
4.
Mucous macroaggregates, recently observed in the northern Adriatic in summer of 1997 and late spring of 2000, are primarily the product of phytoplankton (diatom) exudates during favourable environmental conditions in late spring, and can be viewed as macrogels. The FT-IR and 1H-NMR spectra of macroaggregate samples from the northern Adriatic, collected in different formation stages in July 1997, August 1997, September 1997 and June 2000, as well as of cultured diatom Skeletonema costatum, showed that they are similar and composed of aliphatic components and polysaccharides bonded through carboxylic and amide groups, and organosilicon compounds. The stability of macrogels of macroaggregates is, according to FT-IR and X-ray analyses, most probably enhanced by interactions with entrapped particles of calcite, quartz and clay minerals. These organic-mineral associations seem to be important for mucous phenomena. According to 1H-NMR spectra, the temporal differences in macroaggregate composition show a relative increasing percentage of organosilicon compounds and aliphatic components bonded to carbohydrates through ester and amide groups, and an increasing ratio between aliphatic structures and carbohydrates. This indicates that aliphatic chains bonded to Si and carbohydrates may contribute to the persistence and stability of macroaggregates in the summer stratified waters in the northern Adriatic, while the temporal decrease of carbohydrate content is most probably due to microbial and photochemical degradation of algal reserve polysaccharides.  相似文献   
5.
6.
The role of suspended particulate matter (SPM) as an important carrier of mercury (Hg) dispersed into the Gulf of Trieste and in the adjacent Grado lagoon (Northern Adriatic Sea) was studied during a high Isonzo River inflow and the resulting river plume formation. Despite the fact that extreme flood events are rare during the year, they account for most of the PHg influx (37-112 ngL(-1)) into the Gulf of Trieste. When the river plume is diverted to the SW under the influence of an E-NE wind, the tidal flux acts as a "transport belt" carrying the PHg, mostly inorganic, into the Grado lagoon. A preliminary estimation indicates that the amount of PHg entrapped in the lagoon basin following a tidal semi-cycle accounts for 1.4 kg/12h, which corresponds to about 49% of the total Hg carried by the tidal flow. These findings should be considered in future remediation strategies in the lagoon environment.  相似文献   
7.
Carbon and nitrogen stable isotope ratios of particulate organic matter (POM) were studied approximately weekly during spring and summer 2003 and 2004 in the Gulf of Trieste (northern Adriatic Sea) in order to track the temporal variations and differences between two years. In parallel, particulate organic carbon (POC) and particulate nitrogen (PN), phytoplankton biomass (chlorophyll a), and N and P nutrients were monitored. All studied parameters, especially N and P nutrients and chlorophyll a, showed higher concentrations and larger variability in spring 2004. As a consequence the macroaggregates were produced in late spring 2004. The C and N isotope composition of POM was not directly linked to phytoplankton biomass dynamics. The δ13CPOC values covaried with temperature. In 2004, δ13CPOC variations followed the δ15NPN values as well as the δ13CDIC values which were probably more dependent on the photosynthetic use of 12C. Variations in δ15NPOM values were most probably the consequence of variations in N nutrient sources used in phytoplankton assimilation. The significant correlation between δ15NPN values and nitrate concentrations in 2004 implies intense nitrate assimilation in the presence of higher nitrate concentration. This suggests nitrate as the key nutrient in the »new primary production«, later producing macroaggregates with a mean δ13C and δ15N values of − 19‰ and 5‰, respectively. A low fractionation factor ε, < 1‰, lower than that reported in other marine and lacustrine systems, was found probably to be a consequence of distinct phytoplankton species, i.e. several classes of autotrophic nanoflagellates, and specific growth conditions present in the Gulf of Trieste. The tentative use of C isotope composition of POM revealed a higher contribution of allochthonous organic matter in 2004 compared to 2003 due to higher riverine inflow.  相似文献   
8.
The composition, distribution and the sources of polycyclic aromatic hydrocarbons (PAHs) in the surficial sediments of the Gulf of Trieste were investigated. To document the spatial PAH input, surficial sediment samples from 17 locations throughout the Gulf were analysed. The total PAH load determined in the surficial sediment samples are between 30 and 600 ng g-1, and were the highest in the immediate vicinity of the Port of Trieste. The PAH contents decline rapidly with increasing distance from the shore. The ratios of methylphenanthrenes/phenanthrene and methylpyrene/pyrene are sensitive indicators of the origin of PAH pollution in the Gulf which is mostly pyrolitic. The phenanthrene/anthracene ratio was used to determine the approximate location and distance from the source of PAH pollution, while 1-methy 1-7-isopropylphenanthrene (retene) was used as indicator for forest fires. A sediment depth profile indicates a major increase in the PAH concentrations after the First World War.  相似文献   
9.
Previous research recognized most of the Northern Adriatic coastal lagoon environments as contaminated by mercury (Hg) from multiple anthropogenic sources. Among them, the Pialassa Baiona (P.B.) Lagoon, located near the city of Ravenna (Italy), received between 100 and 200 tons of Hg, generated by an acetaldehyde factory in the period 1957-1977. Further east, the Grado Lagoon has been mainly affected by a long-term Hg input from the Idrija mine (western Slovenia) through the Isonzo River since the 16th century. Hg cycling at the sediment-water interface (SWI) of the two lagoons was investigated and compared by means of an in situ benthic chamber, estimating diffusive Hg and Methyl-Hg fluxes in the summer season. Major chemical features in porewaters (Fe, Mn, H2S, dissolved inorganic (DIC) and organic carbon (DOC), nutrients) and in the solid phase (Corg, N and S) were also explored to understand the general biogeochemical conditions of the system in response to benthic respiration. The daily integrated flux for the methylated Hg form was extremely low in P.B. Lagoon, accounting for only 7% of the corresponding flux calculated for the Grado Lagoon. Despite a higher sedimentary Hg content in the P.B. Lagoon (14.4-79.0 μg g−1) compared to the Grado Lagoon (10.7-12.5 μg g−1), the in situ fluxes of Hg in the two experimental sites appeared similar. A selective sequential extraction procedure was applied to the solid phase, showing that the stable crystalline mineral phase cinnabar (HgS) is the predominant Hg fraction (about 50%) in the Grado Lagoon surface sediments. Conversely, Hg mobilization and sequestration in the P.B. Lagoon is related to the extremely anoxic redox conditions of the system where the intense sulfate reduction, by the release of sulfur and the formation of sulfides, limits the metal recycling at the SWI and its availability for methylation processes. Thus, the environmental conditions at the SWI in the P.B. Lagoon seem to represent a natural “barrier” for the potential risk of Hg transfer to the aquatic trophic chain.  相似文献   
10.
Variations of nitrogen and phosphorus concentrations in the vicinity of Piran (North Adriatic) submarine sewage outfall were studied as well as the treatment plant operation. On the basis of the data it was concluded that the influence of the outfall to the nutrient level in that area is negligible. In comparison the data from the shallow organically polluted water in the inner part of the Bay of Koper are reported.  相似文献   
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