Biomonitoring of trace elements with lichens in Veneto (NE Italy)

The concentrations of 13 elements in peripheral parts of the epiphytic lichen Xanthoria parietina were measured at 200 stations of Veneto (NE Italy). For each element, two maps are presented, showing, respectively, geographic patterns and deviations from background levels. The results are summarized by a map, showing the joint distribution of elements with concentrations close to Italian backgrounds, and of those strongly deviating from background levels. The results allow selection of high-risk areas for instrumental monitoring.     

Concentration and fate of trace metals in Mekong River delta

In the Mekong River delta and its associated coastal zone trace elements concentrations (Cd, Cu, Ni and Pb) were measured in the dissolved phase (DP) during dry (March 1997) and wet (October 1997) seasons. As, Co, Cr, Ni, Pb, and Al were also measured in suspended matter (SM) and total and organic carbon, trace elements (Cd, Cr, Cu, Hg, Mn, Ni, Pb, Zn) and macro elements in superficial sediments (S). Trace metal concentrations in DP and SM during the contrasting hydrological conditions were generally found within the range observed for uncontaminated environment. The average DP concentrations (nM) in the river for March and October are: Cd 0.03 and 0.09, Cu 15 and 14, Ni 7.8 and 8.4, Pb 0.51 and 0.50, respectively. In general there is no significant difference between the concentrations observed during dry and wet season. The evolution of the DP trace metal concentration in the surface water within the salinity gradient suggests no noticeable exchange between the particulate and dissolved phase. This result is in good agreement with those observed in most plume structures studied so far. The average concentrations in the SM (microg/g) (March, October) at the river end-member are: As (24; 11), Co (17; 9), Cr (49; 29), Ni (32; 18), Pb (42; 19) and Al (113,000; 67,000), respectively. All trace elements show higher concentrations in March than in October, with an average increase of two times. This is essentially related to grain size effect since smaller particles were supplied during dry season. These differences are not reflected in the mixing zone, which integrates the seasonal variations. The concentration of major elements (C total, C organic, Si, Al, Ca, K, Fe, Mg, Ti), trace elements (Pb, Zn, Cu, Ni, Mn, Cr, Cd, Hg) in superficial sediments, show similar values during the two seasons and does not show any important variation with depth, indicating either a very fast sedimentation rate and/or the absence of any significant contamination.     

Assessment of mercury and methylmercury pollution with zebra mussel (Dreissena polymorpha) in the Ebro River (NE Spain) impacted by industrial hazardous dumps

Large amounts of industrial waste containing high concentrations of mercury (up to 436 microg/g) are dumped in a reservoir adjacent to a chlor-alkali plant in Flix (Catalonia, Spain), on the lower Ebro River. In order to assess the spatial redistribution of mercury from the point source and its bioavailability to the aquatic food web, zebra mussels (Dreissena polymorpha) were collected at several sites. The highest total Hg (THg) and methylmercury (MeHg) concentrations ever reported for zebra mussels were found (THg: 0.02 to 0.81 microg/g ww; MeHg: 0.22 to 0.60 microg/g ww). At the most polluted site, close to the waste dump, the mean values were 20 times greater than the local background level. Concentrations decreased with increasing mussel size at all sites. The MeHg/THg ratio was ca. 60% (range: 50-80%). A comparison of similar size classes clearly indicated the hot spots of Hg bioavailability to the aquatic food web and downstream transport.     

Biodiversity of epiphytic lichens and heavy metal contents of Flavoparmelia caperata thalli as indicators of temporal variations of air pollution in the town of Montecatini Terme (central Italy)

The results of a biomonitoring survey carried out in the town of Montecatini Terme (central Italy) in the period 1993-2000 using the biodiversity of epiphytic lichens and the accumulation of heavy metals in thalli of Flavoparmelia caperata as indicators of air pollution are reported. From 1993 to 2000, the mean ILD value for the whole study area increased from 18+/-18 to 42+/-22, the lowest ILD value increased from 0 to 11 and the highest ILD value increased from 67 to 84. A 'lichen desert' was found only in 1993 and stations classified as 'natural' were lacking only in 1993 and 1996. Concentrations of all heavy metals decreased from 1993 to 1999. It is concluded that vehicular traffic is the main source of atmospheric pollution in the study area. The most likely changes that may have caused lichen communities to improve and heavy metals to drop is conversion of heating systems to methane (abatement of SO2) and the use of unleaded gasoline (reduction of Pb). The present results showed that despite their slow growth rate, lichens respond rapidly to decreasing concentrations of air pollutants, allowing annual changes to be detected.     

First observation of intersex cyprinids in the Po River (Italy)

Barbel (Barbus plebejus, Cyprinidae) were captured in the Po River, upstream and downstream from the confluence of the Lambro River, a polluted tributary of the major Italian watercourse. The gonads of the two groups of barbel have been histologically examined, and only the downstream specimens showed histo-morphological alterations that can be related to the Lambro tributary as a source to the main river of endocrine disrupting chemicals, possibly with estrogenic effects. In fact, 50% of the barbel captured (8 of 16 fish) in the downstream reach showed intersex gonads.     

Complexation of trace metals by ethylenediaminetetraacetic acid (EDTA) in natural waters

EDTA was determined in detergents, in primary and secondary sewage and in river water. A method for calculating the extent of complexation of trace metals by EDTA in the presence of calcium and other complexing agents is presented. Possible effects on the behaviour of trace metals in the context of sewage treatment, mobility in watercourses, and toxicity to aquatic organisms and in chemical analysis are discussed.     

Biomonitoring of trace metals in the Black Sea (Romania) using mussels Mytilus galloprovincialis

In a preliminary biomonitoring study, accumulated trace metal concentrations (Cd, Cu, Zn, Hg, Fe, Mn) have been measured in the mussel Mytilus galloprovincialis collected in the Black Sea, at 100 km from the Danube Delta in February 2001 and February 2002. Mussels were collected from four sites. In 2001 metal concentrations were determined in the whole soft body whereas, in 2002, the distribution of metals was evaluated in three different organs (gills, visceral mass and remaining tissues). The results obtained in 2002 confirmed those of 2001. For a given site, concentrations were always higher in the gills and visceral mass of mussels than in the remaining tissues. Principal component analysis allowed separating stations as a function of the metal concentrations in the organs. It is concluded that the mussels M. galloprovincialis are suitable biomonitors to assess changes in metal pollution in this coastal area of the Black Sea.     

Quality assessment of bed sediments of the Po River (Italy)

Comprehensive and contemporary evaluations of physical, chemical and toxicological endpoints have been performed on bed sediments of the Po River, the major Italian watercourse. Two extensive sampling campaigns were conducted in summer and winter low-flow conditions. Composite sediment samples were collected from ten reaches of the main river: the first was located in the upper region (ambient control), and the others downstream of the confluences of nine principal tributaries. The two sampling programs were paralleled by contemporary investigations on the macroinvertebrate community. The particle-size composition along the Po River showed a relatively uniform distribution of fine sand, a progressive downstream decrease of coarse sands and a corresponding increase of fine materials. The levels of polychlorinated biphenyls (PCB), polycyclic aromatic hydrocarbons (PAH), extractable organo halides (EOX), Cd, Cr, Cu, Hg, Ni, Pb and Zn were determined in sediment fine particles (< 63 microm), and showed marked changes across the ten river reaches. Their longitudinal trends, as those of organic carbon and total nitrogen, were very similar and largely independent of the survey season. Sediment quality benchmarks were used to evaluate sediment chemistry, and, although the overall level of contamination was from moderate to low, the reaches located downstream of the tributaries Dora Riparia, Dora Baltea, Lambro and Oglio were considered to be at risk. Sediments were tested for toxicity on Oncorhynchus mykiss, Ceriodaphnia dubia, Raphidocelis subcapitata and Vibrio fischeri. The toxicity tests were conducted both with sediment extracts and whole samples. Sediment extracts showed toxic potentials that were consistent with the spatial distribution of contaminants. Whole-sediment toxicity showed moderate/low effects which also included false positives and negatives. Alterations of the macroinvertebrate community were found for many kilometers downstream of Dora Riparia, and with a seasonal dependence, also in other reaches of the Italian river. Principal component analysis (PCA) was used to describe the longitudinal and temporal changes of the Po River, and allowed the selection of the most useful and discriminating indicators.     

Biomonitoring of maritime pollution by heavy metals (Pb and Zn) in the coast of Jijel (Algeria)

This paper reports a study of pollution in the coastal waters of Jijel, Algeria, using algae Ulva lactuca and Corallina officinalis as bioindicators. Samples of seawater and algae were collected at four different stations from the coast of Jijel, during the period of April–June 2014. The heavy metal content (Pb and Zn) was determined in seawater and in the algae tissue by the technique of atomic absorption spectrophotometry. In seawater, the contents of heavy metals vary from 0.017 to 0.03 mg/l (Pb) and 0.235 to 0.873 mg/l. In the algae tissues, metals concentrations vary between 1.88 to 6.25 μg g^?1 dry weight (Pb), and from 92 to 178.9 μg g^?1 dry weight (Zn). These levels differ by site and species. The calculation of the bioconcentration factor (BCF) leads us to conclude that algae bioaccumulate significant levels of Pb and Zn metals in their tissues. Our results shows that the species of C. officinalis bioaccumulate the metals Pb and Zn more than U. lactuca, where, high biosorption of Zn was observed with BCF values between 203.21 and 238.40. Zn content in seawater and algae tissues appear higher than standards set by USEPA and guides values of Certified Reference Materials, but Pb levels appear lower than this standard.     

The performance of two lichen species as bioaccumulators of trace metals

Epidemiological evidence of lung cancer risk from radon is based mainly on studies of men employed underground in mines where exposures are relatively high in comparison to indoor exposure. Nevertheless, direct evidence of risk from residential radon is desirable. In 1990, a study was started comprising 12,000 inhabitants of an area with elevated radon concentrations. The mean level in the houses was higher than general mean of the country by a factor of five. In the period 1961-1995, a total of 173 lung cancers were observed. Comparing to nationally expected numbers (E), the observed number (O) of cases is elevated (O/E = 1.11), in contrast to generally low figures for cancers other than lung (O/E = 0.85). Lung cancer risk related to cumulative exposures experienced in the past 5-24 or 5-35 years were both significant. In relation to standard radon progeny concentration 100 Bq/m3, the excess relative risk coefficient was 0.103 (95% CI, 0.039-0.168), the value somewhat lower than findings in other indoor studies.     

Atmospheric pollution for trace elements in the remote high-altitude atmosphere in central Asia as recorded in snow from Mt. Qomolangma (Everest) of the Himalayas

A series of 42 snow samples covering over a one-year period from the fall of 2004 to the summer of 2005 were collected from a 2.1-m snow pit at a high-altitude site on the northeastern slope of Mt. Everest. These samples were analyzed for Al, V, Cr, Mn, Co, Ni, Cu, Zn, As, Rb, Sr, Cd, Sb, Pb, and Bi in order to characterize the relative contributions from anthropogenic and natural sources to the fallout of these elements in central Himalayas. Our data were also considered in the context of monsoon versus non-monsoon seasons. The mean concentrations of the majority of the elements were determined to be at the pg g(-1) level with a strong variation in concentration with snow depth. While the mean concentrations of most of the elements were significantly higher during the non-monsoon season than during the monsoon season, considerable variability in the trace element inputs to the snow was observed during both periods. Cu, Zn, As, Cd, Sb, and Bi displayed high crustal enrichment factors (EF(c)) in most samples, while Cr, Ni, Rb, and Pb show high EF(c) values in some of the samples. Our data indicate that anthropogenic inputs are potentially important for these elements in the remote high-altitude atmosphere in the central Himalayas. The relationship between the EF(c) of each element and the Al concentration indicates that a dominant input of anthropogenic trace elements occurs during both the monsoon and non-monsoon seasons, when crustal contribution is relatively minor. Finally, a comparison of the trace element fallout fluxes calculated in our samples with those recently obtained at Mont Blanc, Greenland, and Antarctica provides direct evidence for a geographical gradient of the atmospheric pollution with trace elements on a global scale.     

Lichen (Xanthoria parietina) biomonitoring of trace element contamination and air quality assessment in Pisa Province (Tuscany, Italy)

In the northern part of Pisa Province (Tuscany, Italy), the use of lichens as both airborne trace element biomonitors and air quality bioindicators is described. The following elements were analysed in Xanthoria parietina: As, Cd, Cr, Ni, Pb, V, Zn and Hg, and the results are compared with those we previously obtained in Livorno Province (Tuscany) using the same lichen species. The results identify spots of different environmental metal contamination and air quality. Median values of Pb, V and Ni concentrations were much lower than those of Livorno Province, with maximum values even nine times lower. Arsenic contamination was also lower, while Cd, Hg and Zn levels were similar in the two areas. In Pisa Province, the highest levels of contamination were recorded for Zn, Pb, Cr and Ni, and a degree of agreement was found between air quality and metal concentrations in lichens. The air quality in Pisa Province is better than in Livorno Province, even if the different climatic and orographic features of the two areas may influence the presence of lichen species and thus an assessment of air quality.     

Calcite saturation in the River Dee,NE Scotland

The spatial and temporal variations in calcite (calcium carbonate) solubility within the Dee basin of NE Scotland were assessed using water chemistry data gathered from a network of 59 sites monitored for water quality from June 1996 to May 1997. Calcite solubility, expressed in terms of a saturation index (SI_calcite), was determined from measured streamwater pH, Gran alkalinity and calcium concentrations and water temperature. In general, the waters of the Dee system are undersaturated with respect to calcite, though the saturation index is higher during the summer months indicating a dependency on flow conditions and biological activity. Under low-flow conditions, the streamwaters are dominated by water derived from the lower soil horizons and deeper groundwater stores and therefore, ions such as Gran alkalinity and calcium are at their highest concentrations as they are derived mainly from bedrock weathering. The influence of biological activity on the carbonate system is also evident as the observed pH and estimated EpCO₂ values indicate strong seasonal patterns, with the highest pH and lowest EpCO₂ values occurring during the summer low-flow periods. Only at three sites in the lowland region of the catchment, during the summer low-flow period, are the waters oversaturated. As such, the Dee system represents an extreme ‘end-member’ case when compared to many UK rivers that span both under- and oversaturated conditions during the year. Regression analysis highlights a systematic change in the SI_calcite–pH relationship in a broad east-west direction across the Dee system. At sites draining the relatively impermeable upland areas, the regression of SI_Calcite against pH gives a straight line with a gradient in the range 1.6–2.4. Correspondingly, under the most extreme alkaline conditions found at sites draining lowland agricultural areas, a straight-line relationship exists but with a gradient of unity. It is concluded that these changes in the SI_calcite–pH relationship are due to variations in the bicarbonate system induced by the flow conditions and biological activity. Given the waters are undersaturated, then calcite precipitation and hence phosphorus co-precipitation cannot occur within the water column.     

Marine dinoflagellate cysts as indicators of eutrophication and industrial pollution: a discussion

The results from an investigation of dinoflagellate cysts as indicators of eutrophication in Tokyo Bay, Japan, by Matsuoka [Sci Total Environ 231 (1999) 17] are discussed with reference to other pertinent literature not discussed in the original article. Both the Japanese study and previous work from Norwegian fjords show that pollution (including cultural eutrophication) may produce changes in the phytoplankton reflected by a shift from more autotrophic--to more heterotrophic--dominance of cyst assemblages. However, this is a proportional change that seems likely to result from reduced autotrophic production rather than the increased heterotrophic production suggested by Matsuoka. This is not unequivocal evidence of eutrophication, since Tokyo Bay is impacted also by heavy industrial pollution, the possible effects of which cannot be distinguished, and the quantitative method used for estimating changes in cyst productivity is flawed.     

Heavy metals in benthic foraminifera from the highly polluted sediments of the Naples harbour (Southern Tyrrhenian Sea, Italy)

A systematic investigation evaluated the concentrations of a selected number of trace elements (Cd, Co, Cu, Li, Ni, Pb, V and Zn) in carbonates of the benthic foraminifera Ammonia tepida collected from surface sediments of the highly polluted harbour of Naples. Application of cleaning procedures, combined with Scanning Electron Microscopy investigation (SEM) of the analysed shells allowed reliable quantification of the elements in the carbonate lattice. Adoption of biogenic carbonate/seawater distribution coefficients reported in the literature provided the ranges of variability of total dissolved trace elements in the studied marine environment. Very high concentrations of Zn, Cd, and Cu calculated in seawater (from 100 to 10,000 times higher than those reported for uncontaminated Mediterranean seawaters) testify to intense effects of anthropogenic impact on the harbour mainly related to the industrial and commercial activities carried out in the neighbouring area. The ensemble of the obtained results emphasizes the high potential of measurements of trace elements in the biogenic carbonates of benthic foraminifera as tracers of anthopogenic pollution of seawater and reliable proxies of potentially bioavailable forms (as free ions and/or more labile organic complexes) of seawater dissolved metals.     

Electrochemical speciation of trace metals in sea water

Various approaches, such as bioassays, computer-assisted modelling and direct measurement following physical separation are currently being used to investigate the speciation of trace metals in sea water. The electrochemical techniques used successfully as a necessary prerequisite for the experiments involved include conventional polarography, anodic stripping voltammetry (ASV) and potentiometry. Differential pulse anodic stripping voltammetry (DPASV) using mercury film electrodes enables direct studies in ultratrace levels present in non-contaminated ocean waters.By varying the conditions of the sample chemistry and electroanalysis it is possible to characterize metal-organic interactions. This is demonstrated in the case of natural sea water samples subjected to ASV diagnosis. Differences in the Pb and Cu values yielded for Baltic waters by two methods based on DPASV and AAS are discussed with regard to speciation.An analysis of the existing literature is used to briefly summarize the needs of future research. Important problems requiring a more precise quantitative analysis include the adsorption of organics on electrodes and the kinetics and thermodynamic constants of chelates with special regard to the physico-chemical nature of metal-humic substances. The introduction of new and improved electroanalytical techniques and equipment for speciation studies is strongly recommended.     

Metallothioneins (MTs) and delta-aminolevulinic acid dehydratase (ALAd) as biomarkers of metal pollution in great tits (Parus major) along a pollution gradient

Biomonitoring allows an integrated evaluation of different aspects of exposure, accumulation and effects to environmental pollution, simultaneously accounting for the natural variety between individuals in an ecosystem. In this study, the effects of increased metal accumulation were evaluated at the biochemical level in terms of two biomarker responses in the great tit (Parus major), a small insectivorous songbird, along an established metal pollution gradient. Metal concentrations in internal tissues (liver and kidney) and blood indicated that lead and cadmium were the most important metals in the pollution gradient under study. At the biochemical level, induction of metal binding protein metallothionein (MT) in liver and kidney reflected cadmium concentrations in these tissues (R(2)=0.42 and R(2)=0.94 respectively, n=19), although in kidney, MT induction was not sufficient to complex all cadmium present. Secondly, the activity of the enzyme delta-aminolevulinic acid dehydratase (ALAd) in blood decreased exponentially in response to increased lead accumulation (R(2)=0.70, n=18) and represents therefore a specific effect marker for lead exposure. In the highest polluted area, an ALAd inhibition of 85% was reported. Since a higher metal exposure resulted in an increased metal accumulation and subsequent biomarker responses in a dose-dependent way, this study indicates the applicability of ALAd and MT levels in great tits for biomonitoring responses to heavy metal pollution.     

The use of the red swamp crayfish (Procambarus clarkii, Girard) as indicator of the bioavailability of heavy metals in environmental monitoring in the River Guadiamar (SW, Spain)

A translocation experiment of red swamp crayfish (Procambarus clarkii) to different sites located in the River Guadiamar was performed in order to assess the ability of this species as bioindicator of heavy metal and metalloid contamination. Crayfish were placed in cages and exposed to polluted environment during either 6 or 12days in the three sites with different concentration of contaminants. Their tissues (exoskeleton+gills, hepatopancreas and abdominal muscle) were dissected and analysed by ICP-MS to assess for concentration of Cd, Cu, Zn, Pb and As. Both exposure times result in significant bioaccumulation of some metals in crayfish tissues as compared to their concentration in the environment. According to overall metal concentration, crayfish tissues rank as follows: hepatopancreas/viscera>exoskeleton/gills>abdominal muscle. Essential metals for crayfish metabolism (Cu and Zn) are always found in high concentrations independently of their quantities in the environment because of the ability of crayfish to manipulate their levels for their own metabolic profit. Metals not involved in crayfish metabolism (Cd, Pb, As) tend to increase with increasing concentration in the surrounding environment and with longer exposure times. Thus crayfish could be used as bioindicator of these pollutants because their dose- and time-dependent accumulation may be reflective of the levels of non-essential metals present in contaminated wetlands. Future guidelines in plans for monitoring contamination on polluted Mediterranean rivers and wetlands should take into account the implementation of the incubation of crayfish during 6days and their subsequent analyses of metal contents, as a routine.     

Land inputs of trace metals, major elements, particulate organic carbon and suspended solids to an industrial coastal bay of the NE Atlantic

Rivers, streams and municipal and industrial effluents flowing into the Ferrol Ria (NW Spain) were analyzed for dissolved and particulate trace elements (Cd, Cu, Pb, Zn), particulate major elements (Al, Fe, Si), particulate organic carbon and nitrogen (POC and PON), and total suspended solids. Trace metal clean techniques were applied. Mean annual fluxes of these components were calculated. Dissolved trace metal concentrations in the major freshwater inputs were found to be within typical values for uncontaminated rivers: Cd: 0.020-0.035 nM; Cu: 11.7-19.2 nM; Pb: 0.40-0.71 nM and Zn: 18-54 nM. Two sources of suspended particulate matter (SPM) were observed: (i) a detrital SPM, which becomes more important at high river discharges, with metal concentrations tending to lithogenic values; (ii) an organic- and metal-rich SPM, which becomes dominant at low discharges. Municipal and industrial effluents in the northern shore, despite of constitute a minor freshwater contribution to the bay, were responsible for more than 50% of total inputs of Cu, Cd, Pb, Zn, POC and PON. The fluxes of trace metals obtained for the Ferrol Ria are in the range of other inhabited world semi-enclosed embayments.     

PCB pollution behaviour in the River Seine

The contamination of the River Seine (France) and its main tributaries (Yonne, Marne, Oise) have been studied, under different hydrological conditions, at the end of spring before the low watermark and at the beginning of autumn after the first swelling of flow.The sector under study consists of the Seine basin, centered on the Paris area; the variability of PCB concentration in water, apart from flow dependence, shows that important lateral discharges are involved. The pollution level is particularly noticeable at Paris and downstream from Paris and the median concentration in sediments reaches 3800 ng l⁻¹ (ppb). Data on particulate organic carbon and various grain size fractions show the PCB to be preferentially adsorbed on organic-rich sedimentary particles.Partition coefficients between particulate matter and liquid phase have been computed and show that the liquid phase has the main role in micropollutant transport.