Measuring acid volatile sulphide in floodplain lake sediments: effect of reaction time, sample size and aeration

For the routine measurement of acid volatile sulphide (AVS) in floodplain lake sediments, an earlier published diffusion method was adapted and optimised. We evaluated the effect of reaction time, sample weight and passive sample aeration on AVS recovery, and determined the method's reproducibility. The optimal reaction time was 4 h. Losses of AVS due to sample aeration did not occur within 15 min of sample-air contact. Relative standard deviation was <2.5% for known sulphide solutions, was between 10% and 15% for AVS concentrations in sediments and <12% for SEM concentrations in sediments, generally. Sediment samples with known SEM and AVS content were used to compare results of the developed method with the purge-and-trap method. There is a good agreement with the purge-and-trap method for SEM concentrations. AVS concentrations measured with the diffusion method are higher than with the purge-and-trap method. We conclude that the adapted diffusion method is well suited for the routine measurement of AVS concentrations in floodplain sediments.     

Chlorine,Bromine AND Iodine in arctic aerosols

Weekly suspended particulate samples were collected at three stations in the Canadian Arctic between 1979 and 1984. The halogens, Cl, Br and I were determined, along with a comprehensive suite of elements and ions. As was previously observed in Alaska, Br was found to peak every year just after the Arctic dawn, reaching concentrations of two orders of magnitude greater than could be explained by marine, automotive and crustal sources. Chlorine concentration correlated closely with that of Na, indicating a marine origin. It was found to be strongly depleted relative to Na during periods of high sulphate concentration. Iodine was found to be enormously enriched relative to seawater by a factor of 1000 –10,000. The enrichment was least during the early winter when marine aerosol concentrations were at their highest. At locations remote from open oceans I concentrations exhibited two annual peaks, one in the spring, and one during the early autumn. No clear correlations with other parameters could be found for these peaks. At locations close to open ocean, concentrations were higher than at the inland sites and did not vary seasonally.     

Metal accumulation in earthworms inhabiting floodplain soils

The main factors contributing to variation in metal concentrations in earthworms inhabiting floodplain soils were investigated in three floodplains differing in inundation frequency and vegetation type. Metal concentrations in epigeic earthworms showed larger seasonal variations than endogeic earthworms. Variation in internal levels between sampling intervals were largest in earthworms from floodplain sites frequently inundated. High and low frequency flooding did not result in consistent changes in internal metal concentrations. Vegetation types of the floodplains did not affect metal levels in Lumbricus rubellus, except for internal Cd levels, which were positively related to the presence of organic litter. Internal levels of most essential metals were higher in spring. In general, no clear patterns in metal uptake were found and repetition of the sampling campaign will probably yield different results.     

Oxidation of acid-volatile sulfide in surface sediments increases the release and toxicity of copper to the benthic amphipod Melita plumulosa

Acid-volatile sulfides (AVS) are an important metal-binding phase in sediments. For sediments that contain an excess of AVS over simultaneously extracted metal (SEM) concentrations, acute or chronic effects should not result from the metals Cd, Cu, Ni, Pb and Zn. While AVS phases may exist in surface sediments, the exposure to dissolved oxygen may oxidize the AVS and release metals to more bioavailable forms. We investigated the role of oxidation of AVS, and specifically copper sulfide phases, in surface sediments, in the toxicity to juveniles of the epibenthic amphipod, Melita plumulosa. Sediments containing known amounts of copper sulfide were prepared either in situ by reacting dissolved copper with AVS that had formed in field sediments or created in sediments within the laboratory, or by addition of synthesised CuS to sediments. Regardless of the form of the copper sulfide, considerable oxidation of AVS occurred during the 10-d tests. Sediments that had a molar excess of AVS compared to SEM at the start of the tests, did not always have an excess at the end of the tests. Consistent with the AVS-SEM model, no toxicity was observed for sediments with an excess of AVS throughout the tests. However, the study highlights the need to carefully consider the changes in AVS concentrations during tests, and that measurements of AVS and SEM concentrations should carefully target the materials to which the organisms are being exposed throughout tests, which in the case of juvenile M. plumulosa is the top few mm of the sediments.     

Vertical distribution of acid-volatile sulfide and simultaneously extracted metals in mangrove sediments from the Jiulong River Estuary,Fujian, China

Background Acid-volatile sulfide (AVS) is operationally defined as sulfides in sediment, which are soluble in cold acid, and is reported as the most active part of the total sulfur in aquatic sediments. It is a key partitioning phase controlling the activities of divalent cationic heavy metals in sediment. Methods In order to examine this in mangrove environments, six sites were selected along the Jiulong River Estuary in Fujian, China, which had previously been reported to be polluted by heavy metals. Sediments were sampled from 0–60 cm depth at each site, and the spatial distribution of AVS and SEM (simultaneously extracted metals: copper, cadmium, zinc, and lead) were determined. Results and Discussion The results indicate that the AVS concentrations had a spatial variation, ranging from 0.24 to 16.10 μmol g⁻¹ sediment dry weight. The AVS concentration in the surface layer is lower than that of the deeper sediment, with peak values in the 15–30 cm horizon. There was no correlation between the AVS value and organic matter content or total dissolved salts, but a significant positive correlation of AVS with surface sediment (0–5 cm) moisture content was found. This indicates that water logged sediments tend to have a high AVS value. The amount of SEM was within the range of 0.33–2.80 μmol g⁻¹ sediment dry weight and decreased with sediment depth. Conclusions There was a marked variation in AVS and SEM among different sites studied. AVS concentrations were generally lower in the surface sediments, while SEM concentrations slightly decreased with the depth. Higher concentrations of SEM found in the upper layers of the sediments confirm the earlier suggestions that this study area may suffer from increasing heavy metal pollution. Recommendations and Perspectives When monitoring environmental impacts by using AVS, the micro and large-scale spatial variation as well as vertical distribution need to be estimated to avoid misleading results. Both AVS and SEM concentrations in different sediment layers should be taken into account in assessing the potential impact of heavy metals on the biotic environment.     

Passive sampler derived air concentrations of PBDEs along an urban-rural transect: spatial and temporal trends

Passive air samplers consisting of polyurethane foam (PUF) disks housed in chambers were deployed at several sites along a approximately 75 km urban-rural gradient in Toronto and analyzed for polybrominated diphenyl ethers (PBDEs). Samplers were allowed to integrate gas-phase PBDEs over three consecutive seasons starting in the summer of 2000. PBDEs were fairly uniform along the transect with air concentrations in Toronto (10-30 pgm(-3)) about a factor of two greater than at rural sites. Lowest concentrations were observed during the winter and probably associated with reduced inputs from indoor sources of PBDEs and to a preference for PBDEs to partition to the particle-phase at colder temperatures. The composition of PBDEs in the air samples did not differ across the transect or for the different seasons.     

Benzene, toluene, ethyl benzene and xylenes in ambient air and Pinus sylvestris L. needles: a comparative study between Belgium, Hungary and Latvia

Concentrations of benzene, toluene, ethyl benzene and xylenes (BTEX) in ambient air and in 1 yr old Pinus sylvestris pine needles were monitored along a busy road, petrol station and rural area of Belgium, Hungary and Latvia in a 1 yr period. To test P. sylvestris as a possible biomonitor for the BTEX concentrations, samples were taken in the four seasons. As the distribution of data was not normal, the level of pollution on different sites and seasons was compared and evaluated by non-parametric tests. The measured air concentrations did not differ significantly from one season to another throughout the year. There were, however, differences between sampling places. The C₂-alkylbenzene and toluene concentrations in the needles were similar in the autumn/winter and spring/summer periods but a significant decrease in their concentration was observed in every place between winter and spring. This effect was less obvious for toluene.     

Sources of variation in concentrations of nickel and copper in mountain birch foliage near a nickel-copper smelter at Monchegorsk, north-western Russia: results of long-term monitoring

Concentrations of nickel and copper, two principal metal pollutants of the 'Severonikel' smelter at Monchegorsk, NW Russia, were measured in unwashed leaves of mountain birch, Betula pubescens subsp. czerepanovii, collected in eight study sites along the pollution gradient during 1991-2003. In spite of significant decline in metal emissions, concentrations of foliar metals in most of the study sites did not decrease, indicating that soil contamination remains extremely high. Multiyear mean values peaked at 6.6 km S of the smelter, where they were 20-25 times higher than in the most distant study site. Concentrations of both metals demonstrated pronounced annual variation, which was explained by the meteorological conditions of early summer: higher precipitation in May increased foliar concentrations of both metals, whereas higher precipitation in June resulted in lower foliar concentrations of nickel. These data suggest that ecotoxicological situation in metal-contaminated areas can be modified by the expected climate change. In heavily polluted sites individual birch trees generally retained their ranks in terms of metal contamination during 1995-2003, demonstrating that the use of the same set of trees can significantly increase the accuracy of the monitoring data.     

The relation between Acid Volatile Sulfides (AVS) and metal accumulation in aquatic invertebrates: Implications of feeding behavior and ecology

The present study evaluates the relationship between Acid Volatile Sulfides (AVS) and metal accumulation in invertebrates with different feeding behavior and ecological preferences. Natural sediments, pore water and surface water, together with benthic and epibenthic invertebrates were sampled at 28 Flemish lowland rivers. Different metals as well as metal binding sediment characteristics including AVS were measured and multiple regression was used to study their relationship with accumulated metals in the invertebrates taxa.Bioaccumulation in the benthic taxa was primarily influenced by total metal concentrations in the sediment. Regarding the epibenthic taxa metal accumulation was mostly explained by the more bioavailable metal fractions in both the sediment and the water. AVS concentrations were generally better correlated with metal accumulation in the epibenthic invertebrates, rather than with the benthic taxa. Our results indicated that the relation between AVS and metal accumulation in aquatic invertebrates is highly dependent on feeding behavior and ecology.     

Effects of heavy metal exposure on the condition and health of nestlings of the great tit (Parus major), a small songbird species

In this study we examined the possible effects of heavy metal exposure on the condition and health of great tit nestlings (Parus major) at four study sites along a pollution gradient near a large non-ferrous smelter in Belgium during three consecutive breeding seasons. Our results showed that nestlings were indeed exposed to large amounts of heavy metals. Excrements contained significantly higher concentrations of several heavy metals (silver, arsenic, cadmium, mercury, lead) near the pollution source than at study sites farther away. When taking into account the number of young in the nest at the time of sampling, nestling body mass and condition were significantly reduced at the most polluted site. Nestlings at the two most polluted sites fledged significantly later than at the least polluted site. We also observed growth abnormalities of the legs near the pollution source. Tarsus length, wing length and haematocrit values did not differ significantly among study sites.     

Temporal and spatial biomonitoring of heavy metals in Hong Kong coastal waters using Tetraclita squamosa

The barnacle Tetraclita squamosa (Crustacea: Cirripedia) was collected from 11 sites in the coastal waters of Hong Kong during three consecutive seasons, i.e. summer 1996, winter 1996-1997 and summer 1997. Barnacle soft tissues were analysed for cadmium, copper, manganese, iron and zinc using inductively coupled plasma atomic emission spectrophotometry. Analysis of covariance allowed inter-seasonal (temporal) and inter-site (spatial) comparisons of soft tissue metal concentrations to be made, from which bioavailabilities to T. squamosa have been inferred. Inter-seasonal variation was not greater than intra-seasonal and, therefore, seasonal variation in soft tissue metal concentrations can be considered relatively unimportant. Data were, however, characterised by high temporal variability. Spatial variation in metal bioavailabilities were consistent with earlier studies: cadmium soft tissue concentrations were elevated in barnacles collected from low salinity western waters, while copper and zinc concentrations were elevated in the urban-fringed central waters, in particular at one site, i.e. Aberdeen. In general, metal concentrations were much lower in barnacles collected from eastern water sites.     

Resuspension of contaminated field and formulated reference sediments Part I: Evaluation of metal release under controlled laboratory conditions

In aquatic systems where metal contaminated sediments are present, the potential exists for metals to be released to the water column when sediment resuspension occurs. The release and partitioning behavior of sediment-bound heavy metals is not well understood during resuspension events. In this study, the release of Cd, Cu, Hg, Ni, Pb and Zn from sediments during resuspension was evaluated using reference sediments with known physical and chemical properties. Sediment treatments with varying quantities of acid volatile sulfide (AVS), total organic carbon (TOC), and different grain size distributions were resuspended under controlled conditions to evaluate their respective effects on dissolved metal concentrations. AVS had the greatest effect on limiting release of dissolved metals, followed by grain size and TOC. Predictions of dissolved concentrations of Cd, Ni, Pb and Zn were developed based on the formulated sediment Σ_metal/AVS ratios with Σ_metal being the total sediment metal concentration. Predicted values were compared to measured dissolved metal concentrations in contaminated field sediments resuspended under identical operating conditions. Metal concentrations released from the field sediments were low overall, in most cases lower than predicted values, reflecting the importance of other binding phases. Overall, results indicate that for sulfidic sediments, low levels of the study metals are released to the dissolved phase during short-term resuspension.     

Effects of heavy metals on population growth and metallothionein gene expression in the mosquito Culex quinquefasciatus, from Calcutta, India

Major water bodies in and around the city of Calcutta (India) receive heavy metal contaminated effluents from industries, households, and vehicular traffic through sewage or drainage. We quantified concentrations of Cu, Zn, and Cd from three water bodies at Kalighat, Tangra, and VIP Road, respectively. The concentrations of these heavy metals were significantly greater in the summer than in monsoon when heavy downpours resulted in reduced metal concentrations. Concentrations of metals in the mosquito Culex quinquefasciatus also reflected such seasonal fluctuations. Hatchability and survivorship of C. quinquefasciatus significantly differed among the sites and were reduced significantly from the control. Exposure to heavy metals also induced MT-gene expression in C. quinquefasciatus, likely helping them to survive in the water bodies stressed with heavy metals. MT-gene activity demonstrated significant variation among sites and seasons with the highest activity in the summer in the VIP Road population. This study suggests that C. quinquefasciatus could be used as an ecological indicator of heavy metal pollution by monitoring its MT-gene expression.     

Diurnal and seasonal trends in carbonyl levels in a semi-urban coastal site in the Gulf of Campeche,Mexico

Concentrations of formaldehyde, acetaldehyde, acetone, propionaldehyde and butyraldehyde were measured in a semi-urban coastal site in the Gulf of Campeche, Mexico, during the winter, summer and autumn seasons. Measurements were carried out from 10 February 2004 to 16 November 2004. Carbonyl compound levels showed pronounced diurnal and seasonal variations. Maximum concentrations occurred between 13:00 h and 16:00 h, when vehicular traffic and photochemical activity were intense, and during the summer (when there was greater solar radiation). Only acetone during the first campaign (winter) did not correlate with temperature; it showed an inverse diurnal pattern, with higher concentrations during the night, probably due to a local and temporal source. The low concentrations of the main carbonyls found in this study, compared with the values reported for other urban areas, seem to indicate that air quality is still satisfactory in Carmen City.     

Floodplain methylmercury biomagnification factor higher than that of the contiguous river (South River, Virginia USA)

Mercury biomagnification on the South River floodplain (Virginia, USA) was modeled at two locations along a river reach previously modeled for methylmercury movement through the aquatic trophic web. This provided an opportunity to compare biomagnification in adjoining trophic webs. Like the aquatic modeling results, methylmercury-based models provided better prediction than those for total mercury. Total mercury Food Web Magnification Factors (FWMF, fold per trophic level) for the two locations were 4.9 and 9.5. Methylmercury FWMF for the floodplain locations were higher (9.3 and 25.1) than that of the adjacent river (4.6). Previous speculation was not resolved regarding whether the high mercury concentrations observed in floodplain birds was materially influenced by river prey consumption by riparian spiders and subsequent spider movement into the trophic web of the adjacent floodplains. Results were consistent with a gradual methylmercury concentration increase from contaminated floodplain soil, to arthropod prey, and finally, to avian predators.     

Seasonal variations in hepatic Cd and Cu concentrations and in the sub-cellular distribution of these metals in juvenile yellow perch (Perca flavescens)

Temporal fluctuations in metal (Cd and Cu) concentrations were monitored over four months (May to August) in the liver of juvenile yellow perch (Perca flavescens) sampled from four lakes situated along a metal concentration gradient in northwestern Quebec: Lake Opasatica (reference lake, low metal concentrations), Lake Vaudray (moderate metal concentrations) and lakes Osisko and Dufault (high metal levels). The objectives of this study were to determine if hepatic metal concentrations and metal-handling strategies at the sub-cellular level varied seasonally. Our results showed that Cd and Cu concentrations varied most, in both absolute and relative values, in fish with the highest hepatic metal concentrations, whereas fish sampled from the reference lake did not show any significant variation. To examine the sub-cellular partitioning of these two metals, we used a differential centrifugation technique that allowed the separation of cellular debris, metal detoxified fractions (heat-stable proteins such as metallothionein) and metal sensitive fractions (heat-denaturable proteins (HDP) and organelles). Whereas Cd concentrations in organelle and HDP fractions were maintained at low concentrations in perch from Lakes Opasatica and Vaudray, concentrations in these sensitive fractions were higher and more variable in perch from Lakes Dufault and Osisko, suggesting that there may be some liver dysfunction in these two fish populations. Similarly, Cu concentrations in these sensitive fractions were higher and more variable in perch from the two most Cu-contaminated lakes (Dufault and Osisko) than in perch from the other two lakes, suggesting a breakdown of homeostatic control over this metal. These results suggest not only that metal concentrations vary seasonally, but also that concentrations vary most in fish from contaminated sites. Furthermore, at the sub-cellular level, homeostatic control of metal concentrations in metal-sensitive fractions is difficult to maintain in perch with high hepatic metal concentrations.     

Spatial distribution and internal metal concentrations of terrestrial arthropods in a moderately contaminated lowland floodplain along the Rhine River

Soil metal concentrations, inundation characteristics and abundances of 14 arthropod taxa were investigated in a moderately contaminated lowland floodplain along the Rhine River and compared to the hinterland. Internal metal concentrations were determined for the orders of Coleoptera (beetles) and Araneida (spiders) and were related to soil concentrations. The floodplain was characterized by larger arthropod abundance than the hinterland, in spite of recurrent inundations and higher soil metal concentrations. Most arthropod taxa showed increasing abundance with decreasing distance to the river channel and increasing average inundation duration. For Cd, Cu, Pb and Zn, significant relations were found between arthropod concentrations and concentrations in soil. Significant relations were few but positive, indicating that increasing soil concentrations result in increasing body burdens in arthropods. For arthropod-eating vertebrates, these results might imply that larger prey availability in the floodplain coincides with higher metal concentrations in prey, possibly leading to increased exposure to metal contamination.     

Analyses of ozone in urban and rural sites in Málaga (Spain)

Ozone concentrations were measured at two (urban and a rural) sites near the city of Málaga (Spain). The aim of this study was to determine the daily, monthly and seasonal variation patterns of ozone concentrations at both sites and to study the possible regional influences. The daily variations mostly have the usual features with the afternoon maximum and the night minimum being more pronounced in the urban area. The average monthly concentrations throughout the year start to increase in March reaching their maximum values in July for the urban site. However, in the rural area, the monthly variations are smaller reaching their maximum value in June. The hourly evolution of the ozone concentrations in both sampling sites is well defined in spring and summer and not so well defined in autumn and winter. Taking into account the four seasons, the rural concentrations are higher than the urban ones. Summer is the season when there are similar concentrations at both sampling sites. Average hourly summer afternoon ozone for the hours 12:00-20:00 LST exceeded the 110 microg m(-3) European Union guidelines for human health for 8 h ozone exposure at the urban and rural sites.     

Laboratory and field evaluation of measurement methods for one-hour exposures to O3, PM2.5, and CO.

While researchers have linked acute (less than 12-hr) ambient O3, PM2.5, and CO concentrations to a variety of adverse health effects, few studies have characterized short-term exposures to these air pollutants, in part due to the lack of sensitive, accurate, and precise sampling technologies. In this paper, we present results from the laboratory and field evaluation of several new (or modified) samplers used in the "roll-around" system (RAS), which was developed to measure 1-hr O3, PM2.5, and CO exposures simultaneously. All the field evaluation data were collected during two sampling seasons: the summer of 1998 and the winter of 1999. To measure 1-hr O3 exposures, a new active O3 sampler was developed that uses two nitrite-coated filters to measure O3 concentrations. Laboratory chamber tests found that the active O3 sampler performed extremely well, with a collection efficiency of 0.96 that did not vary with temperature or relative humidity (RH). In field collocation comparisons with a reference UV photometric monitor, the active O3 sampler had an effective collection efficiency ranging between 0.92 and 0.96 and a precision for 1-hr measurements ranging between 4 and 6 parts per billion (ppb). The limits of detection (LOD) of this method were 9 ppb-hr for the chamber tests and approximtely 16 ppb-hr for the field comparison tests. PM2.5 and CO concentrations were measured using modified continuous monitors--the DustTrak and the Langan, respectively. A size-selective inlet and a Nafion dryer were placed upstream of the DustTrak inlet to remove particles with aerodynamic diameters greater than 2.5 microm and to dry particles prior to the measurements, respectively. During the field validation tests, the DustTrak consistently reported higher PM2.5 concentrations than those obtained by the collocated 12-hr PM2.5 PEM samples, by approximately a factor of 2. After the DustTrak response was corrected (correction factor of 2.07 in the summer and 2.02 in the winter), measurements obtained using these methods agreed well with R2 values of 0.87 in the summer and 0.81 in the winter. The results showed that the DustTrak can be used along with integrated measurements to measure the temporal and spatial variation in PM2.5 exposures. Finally, during the field validation tests, CO concentrations measured using the Langan were strongly correlated with those obtained using the reference method when the CO levels were above the LOD of the instrument [approximately 1 part per million (ppm)].     

Influence of Spartina alterniflora on the mobility of heavy metals in salt marsh sediments of the Yangtze River Estuary, China

Using bio-disturbed sulphide to trace the mobility and transformation of Cu, Pb, Ni and Zn in the sediments of the Spartina alterniflora-dominated salt marsh in the Yangtze River Estuary, measurements were made of the seasonal variations of acid-volatile sulphide (AVS) and of the simultaneously extracted metals (SEM) in the rhizosphere sediments. Microcosm incubation experiments recreating flooding conditions were conducted to evaluate the effect of AVS and other metal binding phases upon the dynamics of Cu, Pb, Ni and Zn in the salt marsh sediments. The results demonstrate that the ratio values of SEM/AVS have a significant seasonal variation in the rhizosphere sediments and that the anoxic conditions in the sediments were likely enhanced by S. alterniflora during the summer and autumn compared with the anoxic conditions resulting from the native species Phragmites australis and Scirpus mariqueter. The incubation experiments suggest that Fe(III) and Mn(IV/III) (hydr)oxides provide important binding sites for heavy metals under oxic conditions, and sulphide provides important binding sites for the Cu and Pb under anoxic conditions. Our observations indicate that the mobility of heavy metals in the salt marsh sediments is strongly influenced by biogeochemical redox processes and that the invasive S. alterniflora may increase the seasonal fluctuation in heavy metal bioavailability in the salt marsh ecosystem.