Organic pollution in a Ramsar site (Piallassa Baiona, northern Adriatic Sea)

A core collected in the Piallassa Baiona lagoon, a salt-marsh area already studied for Hg contamination related to nearby industrial sites, was analysed for organic micropollutants. Surface sediments show high concentrations of total PCBs (1148 ng g-1), PCDD/Fs (64 ng g-1) and PAHs (4801 ng g-1). According to a sedimentation rate of 0.4 cm y-1, the high increases in total PAH, PCB and PCDD/F concentrations began in the 1960s and peaked in the 1970s, in parallel with the highest Hg concentrations. Instead, the recent contamination, which primarily involves PCBs and PCDD/Fs, has been observed to be unrelated to Hg concentrations. Organic micropollutant concentrations in the sample core were compared with the sediment quality criteria provided by international guidelines, and revealed high toxic potential. This heavy contamination was also confirmed by comparison with similar environments, particularly the Lagoon of Venice. Further investigations are needed to understand better the sources of the recent contamination and to explain the different transfer pathways involved during sedimentation of the "old" material, dumped 20-30 years ago.     

Assessment of heavy metal background values in the soils of inland coastal areas of Venice,Italy

The main aim of this project was to assess background levels of heavy metals in soil in the inland coastal area of Venice, Italy. The pilot study area is located near the industrial area of Porto Marghera, considered of national interest in terms of contaminated soil remediation (Environmental Ministerial Decree n. 471/1999). The Decree under consideration emphasises the importance of the assessment of background values in soil remediation. Results will show cases (As and Sn) in which background values are greater than concentration limit standards given by legislation.     

Occurrence of organochlorine pesticides and polychlorinated biphenyls in soils and sediments from Eastern Romania

Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs), such as DDT and analogues, hexachlorocyclohexane (HCH) isomers and hexachlorobenzene (HCB), were measured in surface soils and sediments from Eastern Romania. Thirty-nine soil samples from the forested zone, eight soil samples from a municipal waste-disposal site, and 10 sediment samples from the Bahlui River along the Iassy city were analysed using accelerated solvent extraction (ASE) and gas chromatography coupled to electron capture detection or mass spectrometry. The low mean concentrations of OCPs (11–31 and 22–84?ng?g^?1 for HCHs and DDTs, respectively) and PCBs (8–43?ng?g^?1) in soil samples from the forested zone suggest that contamination at most of these sites occurred predominantly through atmospheric transport from zones where these compounds were used and subsequently through atmospheric deposition. Contrarily, soil samples collected in the vicinity of a waste-disposal site near Iassy contained higher mean levels of PCBs (278?ng?g^?1, range 34–1132?ng?g^?1) than OCPs (6 and 101?ng?g^?1 of soil for HCHs and DDTs, respectively). The sediment samples collected along the Bahlui river throughout the Iassy city revealed higher mean levels of PCBs (59?ng?g^?1, range 24–158?ng?g^?1) compared with OCP levels (2 and 37?ng?g^?1 of soil for HCHs and DDTs, respectively). Furthermore, PCB profiles and concentrations in the sediment samples varied considerably along the river due to a wide variety of sources, such as different industries and waste sites. Although their sources are difficult to evaluate, the presence of POPs at most sites (especially at the waste-disposal site) may constitute a potential health hazard.     

Study of the interference problems of dioxin-like chemicals with the bio-analytical method CALUX

The reporter gene expression method CALUX has proven to be a very valuable screening technique for assessing toxic equivalents of dioxins and dioxin-like compounds, because it detects all AhR ligands in a variety of sample matrices. However, the exact meaning of the CALUX response is difficult to evaluate for complex mixtures mainly since not all AhR ligands are known and since antagonistic or synergistic effects occurs.

In this paper, non-additive effects on the CALUX response of dioxins were investigated for a limited number of dioxin-like compounds in concentration ranges that are 10²–10⁸ times higher than that of 2,3,7,8-TCDD. Antagonistic effects are detected for three Aroclors (1242, 1254, 1260), Halowax 1014 (PCN), HCB and PBB 169. The ratios, Aroclor/dioxin, Halowax/dioxin and HCB/dioxin, needed to observe an antagonistic effect are 10 000, 5000 and 50 000, respectively. No significant deviation from additivity was observed for Aroclor 5442 (PCT) and PBB 77 in the concentration range investigated.

Two clean-up procedures have also been tested: in some cases the non-additive effects disappeared or were strongly reduced. Using only an acidic silica column, the classical dioxin-like compounds investigated here (PCB, PCT, PBB, PCN, HCB) as well as the dioxins are collected and analyzed altogether in one fraction. Consequently, no major alteration of the non-additive effects is expected. An acidic silica column combined with an activated carbon column allows the separation of PCDD/F and dioxin-like PCB in two different fractions, PBB 169 is completely eluted in the dioxin fraction and PBB 77 is distributed between the PCB and dioxin fraction. HCB is completely separated from the PCDD/F fraction.     

Validation of the CALUX bioassay for the screening of PCDD/Fs and dioxin-like PCBs in retail fish

The chemical-activated luciferase expression (CALUX) assay is a reporter gene assay that detects dioxin-like compounds based on their ability to activate the aryl hydrocarbon receptor (AhR) and thus expression of the reporter gene. In this paper, the CALUX assay was examined for its application in the screening of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dioxin-like PCBs) in retail fish. The sample extracts were cleaned up on a sulfuric acid-silica gel column followed by an activated carbon column, and the AhR activity of the separated PCDD/F and dioxin-like PCB fractions was determined using the assay. The quantitative limit for 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) was 0.98 pg ml(-1) (0.19 pg assay(-1) in the standard curve, corresponding to 0.16 pg g(-1) of CALUX-based toxic equivalency (2,3,7,8-TCDD equivalents) in the tested sample. Recovery tests in which dioxins were added to fish samples resulted in acceptable recoveries (77-117%). The CALUX assay performed well in the analysis of dioxins in fish samples and a comparative study revealed a strong correlation between the CALUX assay and high-resolution gas chromatography-high-resolution mass spectrometry analysis for the determination of PCDD/Fs (r = 0.89) and dioxin-like PCBs (r = 0.91) in retail fish (n = 22). These data revealed that the CALUX assay would be a useful screening method for PCDD/Fs and dioxin-like PCBs in retail fish.     

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.     

GC-MS ultra trace analysis of dioxins produced through hydrothermal gasification of biowastes

Hydrogen gas and the valuable material hydroxylapatite have successfully been produced from biomass wastes by hydrothermal gasification. However, it was expected that toxic compounds might be produced through the reaction. It was therefore important to clarify whether toxic compounds were synthesized in hydrothermal gasification of biowastes since dioxins are categorized among the most toxic compounds for humans. This is particularly true of biomass wastes containing hetero-atoms in organic matrices. In this study, formation of the dioxins polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and certain dioxin-like polychlorinated biphenyls (PCBs) were examined. Chicken manure and cattle manure were tested as real biowastes for hydrothermal gasification and the produced compounds in the liquid and solid phases were analyzed for detection of dioxins by gas chromatography/mass spectrometry (GC/MS). The total toxic equivalent quantities (the total TEQ) of dioxins produced by the hydrothermal gasification were found to be much lower than regulation levels in Japan require and therefore the products require no additional post treatments.     

Ecological and hygienic assessment of the consequences of the pollution with persistent organic compounds of an industrial town (by the example of Usol’e-Sibirskoe): I. Atmospheric air,snow, and soil

Data on PCB and OCP distributions in atmospheric air, snow cover, and soil in Usol’e-Sibirskoe and its suburbs are presented. It is shown PCBs and OCPs are continuing to accumulate in soil as a result of their volatilization from polluted soil at the industrial area, atmospheric transport, and deposition on adjacent territories.     

Persistent organic pollutants in edible fish: a human and environmental health problem

Many persistent organic pollutants (POPs) pose serious health hazards to both the environment and human. Among these, polychlorobiphenyls (PCBs) are probable human carcinogens and can also pose non-cancer health hazards to intellectual functions and the nervous, immune and reproductive systems. The risks and hazards associated with POP residues in tissues are a function of the dioxin-like compound toxicity and an individual's exposure. Fish consumption might become a serious problem because of bioaccumulation as revealed in many studies worldwide.We report data concerning the accumulation and pattern of hexachlorobenzene (HCB), p,p′-DDE and PCBs in edible tissues of commercial fish species (bluefin tuna Thunnus thynnus, swordfish Xiphias gladius, Atlantic mackerel Scomber scombrus) from Italian Seas and of the Antarctic toothfish Dissostichus mawsoni from the Ross Sea (Antarctica). The species analyzed are part of the human diet. 2,3,7,8-TCDD toxic equivalents (TEQs) and tolerable weekly intake (TWI) were also calculated to evaluate the toxic hazard for the population that include them in their diet.Gaschromatography revealed 0.16±0.24 and 0.4±0.2 ng/g wet wt of HCB in Antarctic toothfish and bluefin tuna, respectively. p,p′-DDE concentrations were 38±29 and 31±38 ng/g wet wt in swordfish and bluefin tuna muscle, respectively, and 0.66±0.57 ng/g wet wt in the Antarctic toothfish. PCBs showed higher concentrations and they were 89±82, 80±86 and 5.2±4.0 ng/g wet wt in the muscle of swordfish, bluefin tuna and Antarctic toothfish, respectively. In Mediterranean fish, the most abundant congeners were the most persistent PCB numbers 153, 138, 180, 118 and 170, which accounted for 51% and 47% of the total PCB residue in tuna fish and swordfish, respectively, and 18% in the Antarctic toothfish. TEQs were 1.97 and 4.65 pg/g wet wt in bluefin tuna muscle and gonads, respectively, and 0.11 pg/g wet wt in Antarctic toothfish. The TEQ weekly intake was calculated and values ranged 197–465 pg_TEQ/week when consuming 100 g of Mediterranean fish and therefore lower than the recommended TWI. Those values were higher (788–1860 pg_TEQ/week) than the recommended TWI, if 400 g of fish/week was consumed (with the exception of Antarctic fish).     

Performances and limitations of the HRMS method for dioxins, furans and dioxin-like PCBs analysis in animal feedingstuffs: Part I: Results of an inter-laboratory study

The European strategy for dioxin monitoring of the food chain has defined high-resolution gas chromatography coupled to high-resolution mass spectrometry (HRGC/HRMS) method as the confirmatory method that can provide reliable and comparable results at sub-parts per trillion (ppt) level. This paper describes the first inter-laboratory study on dioxins, furans and dioxin-like PCBs by HRGC/HRMS method in animal feedingstuffs. Two different statistical approaches (ISO 5725 and Cofino’s statistics) were used for the statistical evaluation. For this particular study, the performances of the HRGC/HRMS method seem to be congener-independent in repeatability and reproducibility conditions over a concentration range covering more than four orders of magnitude. Results clearly show the effect of precision loss below 0.1 ppt level per congener in repeatability conditions and below 0.2 ppt level per congener in reproducibility conditions. LODs reported by the laboratories give median values of 0.02 ng/kg for most of the toxic congeners. Relative standard deviation between the laboratories’ mean values using upper-bound approach for TEQ calculation is 6.2%, more than twice the maximum level set at 0.75 ng TEQ/kg of product.     

Behaviors of chemical elements in the atmosphere,Kawasaki, Japan

A total of 19 elements in the samples of atmospheric deposition collected in Kawasaki, Japan, were determined by neutron activation analysis, ICPAES and flame photometry. The amounts of soil dust depositions were larger in springs and those of Sb and Zn depositions were larger in summers than in the other seasons. The values of the enrichment factors were higher for Sb and Zn than for the other elements determined throughout the sampling period. A factor analysis showed that the two elements were characterized as industrial components. Rubber products like tires that contain noncombustibles and rubber accelerators were a possible origin of high concentrations of Sb and Zn in the present samples.     

加速溶剂萃取-FMS净化-高分辨气相色谱-高分辨质谱(HRGC-HRMS)定量测定鱼组织中二(噁)英类多氯联苯

多氯联苯(polychlorinated biphenyls,PCBs)是一类包括209种化合物的持久性有机污染物,是斯德哥尔摩公约中优先控制的12类持久性有机污染物之一,曾经大量生产用于变压器和电容器内的绝缘介质、热交换剂、润滑剂、增塑剂等[1],全球共生产150万吨多氯联苯[2-3]。在209种PCBs中有1     

Ecological assessment of Santa Giusta Lagoon (Sardinia,Italy)

The general environmental conditions of Santa Giusta Lagoon, an important Sardinian coastal lagoon often affected by dystrophic crises, are examined. The study considers both the monitoring data collected over the past ten years on the relevant water quality parameters and the preliminary results on the structure and heavy metal content of the surface sediments of the lagoon. These data emphasised its elevated trophic level, due to the excessive presence of plant nutrients in water, and a relative low level of heavy metal contamination. At the moment, the eutrophy--brought about the urban and industrial wastes from Oristano and Santa Giusta--can be considered the main environmental issue of the lagoon.     

Dioxin analysis in feed: cell-based assay versus mass spectrometry method

In the determination of contaminants (dioxins, polychlorinated biphenyls, polyaromatic hydrocarbons), cell-based assays are useful methods for screening purposes: they are mainly characterized by high sample throughput and lower costs than the Mass Spectrometry (MS)-based methods. Although cell-based assays can be sensitive enough for the determination of dioxins and related substances in agreement with the presently tolerable limits in food and feed (Regulation No. 2375/2001/EC and Directive 2003/57/EC respectively), their lack of specificity make their use rather questionable in control laboratories. In this paper, we present and compare results obtained from the analysis of a limited number of feed samples by both gas chromatography-high resolution mass spectrometry (GC-HRMS) and cell-based assay (DR-CALUX: dioxin responsive-chemically activated luciferase gene expression) methods. The DR-CALUX screening led to less than 10% false non-compliant and no false compliant results. In addition, there is a good correlation between GC-HRMS and DR-CALUX data. However, these preliminary results have to be confirmed on a larger number of samples to demonstrate that total toxic equivalent (TEQ), including dioxins, furans and dioxin-like polychlorobiphenyls (PCBs) can be monitored in feed and food with a cell-based assay. Presented at AOAC Europe/Eurachem Symposium March 2005, Brussels, Belgium     

Heavy metals in marine coastal sediments: assessing sources, fluxes, history and trends

Examples are presented from the Adriatic Sea, the Ligurian Sea and the Venice Lagoon to illustrate different approaches to the study of anthropogenic metals in marine coastal sediments. These examples refer to studies of areal distribution and transport mechanisms, individuation of the sources, sediment dating, chronology of the fluxes, present and past trends. In particular, some of the findings achieved in studying the Venice Lagoon are discussed from the point of view of anthropogenic changes both in sediment composition and contaminant fluxes.     

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.     

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.     

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.     

Comparison of gas chromatography-ion-trap tandem mass spectrometry systems for the determination of polychlorinated dibenzo-p-dioxins, dibenzofurans and dioxin-like polychlorinated biphenyls

Two gas chromatography-mass spectrometry systems equipped with an ion-trap mass analyzer working in tandem mode (GC-MS-MS) were evaluated for the determination of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (PCBs) in food samples. The performance of the two ion-trap instruments, which dispose of an external ion source (ThermoFinnigan GCQ/Polaris) and internal ionization (Varian Saturn 2,200), have been compared in terms of linearity, repeatability, limit of detection and long-term precision. Both instruments provided similar run-to-run and day-to-day precisions, ranging from 2% to 8% and between 2% and 13%, and instrumental limits of detection between 0.09 and 0.36 pg injected for PCDD/Fs and from 0.03 to 0.09 pg injected for dioxin-like PCBs. Although both instruments seem to be suitable for food analysis, only the use of external ionization allowed to achieve reliable results for PCDD/F determination at concentrations close to the maximum residue levels established by the EU for foods. Internal ionization provides high limits of detection (from 10- to 30-fold higher) and worse precision (RSD, 14-43%). In contrast, for dioxin-like PCBs both instruments allowed to obtain excellent results with precisions lower than 15%.     

燃烧排放物中的有毒二噁碤及类二噁碤多氯联苯

本文评述了国内外对二噁碤的研究成果及动向,介绍了二噁碤中的有毒同族体及其毒性当量计算、准确的分析方法、燃烧过程中二噁碤的光降解行为及其降解产物、类二噁碤多氛联苯等内容,引述了90多篇最新的文献及有关图表。