Role of manganese oxides in the exposure of mute swans (Cygnus olor) to Pb and other elements in the Chesapeake Bay, USA

The aims of this study are to estimate exposure of waterfowl to elements in contaminated sediments in the Chesapeake Bay and to consider the potential role of Mn in influencing bioavailability and exposure. Metal concentrations were measured in livers and digesta taken from mute swans living on the Aberdeen Proving Ground, whose sediment had elevated concentrations of Cu, S, Se, Zn, As, Co, Cr, Hg and Pb. Concentrations of only the first four of these elements were elevated in swan digesta. None of the concentrations detected in the digesta or livers of the swans was considered toxic, although the concentrations of Cu and Se were high compared to concentrations of these elements reported in other waterfowl. Lead was found to be scavenged by Mn and Fe oxides from the water and deposited on the surface of vegetation at a reference site. Under some environmental chemical conditions, this is an important route of exposure to Pb in waterfowl, not previously recognized.     

Light-induced disappearance of nitrite in the presence of iron (III)

Understanding of rapid disappearance of nitrite in natural waters and its impact on nitrogen natural cycling has remained limited. We found that NO2- disappeared rapidly in pH 3.2 aqueous Fe(III) solutions both in sunlight and in 356 nm light. Quantum yields of the NO2- loss at 356 nm were 0.049-0.14 for initial levels of 10-80 microns NO2- and 200 microns Fe(III). The NO2- loss (at 356 nm) followed apparent first-order kinetics. The rate constants were 1.3 x 10(-3) (40 microns NO2-) and 4.1 x 10(-4) s-1 (80 microns NO2-) for 100 microns Fe(III), and 2.3 x 10(-3) (40 microns NO2-) and 7.5 x 10(-4) s-1 (80 microns NO2(-1)) for 200 microns Fe(III) (t1/2 = 8.7, 27.9, 5.1, and 15.3 min, respectively). The rate constants were directly proportional to [Fe(III)]0 and inversely proportional to [NO2-]0. Agreement between the rate constants obtained experimentally and those calculated mechanistically supports the hypothesis that NO2- was oxidized to NO2 by .OH radicals from photolysis of FeOH2+ complexes, and at high [NO2-]0 (e.g., 80 microns) relative to [Fe(III)]0, hydrolysis of NO2 or N2O4 to form NO3- and NO2- could be significant. This study showed that light and Fe(III)-induced oxidation of NO2- (rate = approximately 10(-1)-10(-2) microns s-1) was more rapid than its direct photolysis (rate = approximately 10(-4) microns s-1), and the photolysis could be a significant source of .OH radicals only in cases where the Fe(III) level is much lower than the NO2- level ([Fe(III)]/[NO2-] < 1/80). This study suggests that the light and Fe(III)-induced oxidation of NO2- would be one potential important pathway responsible for the rapid transformation of NO2- in acidic surface waters, especially those affected by acid-mine drainage or volcanic activities. This study also may be of interest for modeling certain acidic atmospheric water environments.     

Fate of high loads of ammonia in a pond and wetland downstream from a hazardous waste disposal site

Halls Brook (eastern Massachusetts, USA) is a significant source of total dissolved ammonia (sum of NH(3) and NH(4)(+); (NH(3))(T)) to the Aberjona River, a water body listed for NH(3) impairment on the Clean Water Act section 303(d) list. We hypothesized (1) that (NH(3))(T) in Halls Brook derived from a hazardous waste site via groundwater discharging to a two-basin pond that feeds the brook; and (2) that transport of (NH(3))(T) to the Aberjona River was controlled by lacustrine and wetland processes. To test these hypotheses we measured (NH(3))(T) levels in the brook, the pond, and a wetlands directly downstream of the pond during both dry and wet weather over a ten month period. In addition, we analyzed sediment cores and nitrogen isotopes, and performed mass balance calculations. Groundwater discharge from beneath the hazardous waste site was the major source of (NH(3))(T) (20-67 kg d(-1)) and salinity to the north basin of the pond. The salty bottom waters of the north basin were anoxic on all sampling dates, and exhibited relatively stable (NH(3))(T) concentrations between 200 and 600 mg Nl(-1). These levels were >100-times higher than typical background levels, and 8-24-times above the acute effects level for (NH(3))(T) toxicity. Bottom waters from the north basin continuously spill over into the south basin contributing approximately 50% of the (NH(3))(T) load entering this basin. The remainder comes from Halls Brook, which receives (NH(3))(T) loadings from as yet unknown sources upstream. During storm events up to 50% of the mass of (NH(3))(T) was flushed from the south basin and into the wetlands. The wetlands acted as a (NH(3))(T) sink in dry weather in the growing season and a discharge-dependent (NH(3))(T) source to the Aberjona River during rainstorms.     

Environmental fate and non-target impact of glyphosate-based herbicide (Roundup) in a subtropical wetland

Mai Po Nature Reserve (Hong Kong) is an internationally important wetland for waterbirds. Roundup, a formulation based on glyphosate, has been used to control the widespread weeds within the reserve for many years but the fate and non-target impact of the herbicide is unknown. To fill this knowledge gap, we applied Roundup by hand-held sprayer to an estuarine and a freshwater pond in the dry season of year 2002. The surface water and sediment were sampled routinely for glyphosate concentrations following one month of application. In situ bioassays using local edible fish species were performed along with the herbicide application. Up to 52% of glyphosate in the surface water was transported to the unapplied regions by wind-driven current in the estuarine pond at 1 DPT (day post treatment). For both ponds, glyphosate concentrations in the water decreased rapidly after 1-3 DPT, but then decreased gradually over time. Both physical adsorption to the bottom sediments and microbial degradation are thought to contribute to these decreases. Interestingly, the persistence of glyphosate in the freshwater pond was longer than in the estuarine system, which is likely due to the considerably higher concentrations of chelating metals (i.e. Cu and Fe) present in the sediment (4.5 and 11-fold higher, respectively) which potentially reduced the bioavailability of glyphosate to the microbial decomposers. Lastly, fishes used in the in situ bioassays (both in applied and unapplied areas) showed similar survival rates, indicating that the use of Roundup at the provided application rate posed no serious hazard.     

Toxicity of uranium and copper individually, and in combination, to a tropical freshwater macrophyte (Lemna aequinoctialis)

Copper (Cu) and uranium (U) are of potential ecotoxicological concern to tropical freshwater biota in northern Australia, as a result of mining activities. Few data are available on the toxicity of U, and no data are available on the toxic interaction of Cu and U, to freshwater biota. This study determined the toxicity of Cu and U individually, and in combination, to a tropical freshwater macrophyte, Lemna aequinoctialis (duckweed), in a synthetic soft water (27 degrees C; pH, 6.5; hardness, 40 mg CaCO3 l-1, alkalinity, 16 mg CaCO3 l-1), typical of many fresh surface waters in coastal northern Australia. The growth rate of L. aequinoctialis decreased with increasing Cu or U concentrations, with the concentration of Cu inhibiting growth by 50% (EC50) being 16+/-1.0 microg l-1, with a minimum detectable effect concentration (MDEC) of 3.2 microg l-1. The concentration of U inhibiting growth by 50% (EC50) was 758+/-35 microg l-1 with a MDEC of 112 microg l-1. The EC50 value for the exposure of L. aequinoctialis to equitoxic mixtures of Cu and U was significantly (P0.05) higher than one toxic unit (1.35; 95% confidence interval, 1.18-1.52), indicating that the combined effects of Cu and U are less than additive (antagonistic). Therefore, inhibition of the growth rate of L. aequinoctialis was reduced when Cu and U were present in equitoxic mixtures, relative to individual metal exposures. Since non-additive (e.g. antagonistic) interactions of metal mixtures cannot be predicted using current mixture models, these results have important potential implications for the protection of freshwater ecosystems through the derivation of national water quality guidelines.     

Assessment of trace metal contamination in the core sediment of Ramsar wetland (Kabar Tal), Begusarai,Bihar (India)

Environmental Science and Pollution Research - The concentration of trace metals Mn, Pb, Ni, Zn, and Cu in the core sediment from Kabar Tal wetland was analyzed to understand the level of...     

Characteristics and impacts of trace elements in atmospheric deposition at a high-elevation site,southern China

To investigate the regional background trace element (TE) level in atmospheric deposition (dry and wet), TEs (Fe, Al, V, Cr, Mn, Ni, Cu, Zn, As, Se, Mo, Cd, Ba, and Pb) in 52 rainwater samples and 73 total suspended particles (TSP) samples collected in Mt. Lushan, Southern China, were analyzed using inductively coupled plasma-mass spectrometry (ICP-MS). The results showed that TEs in wet and dry deposition of the target area were significantly elevated compared within and outside China and the volume weight mean pH of rainwater was 4.43. The relative contributions of wet and dry depositions of TEs vary significantly among elements. The wet deposition fluxes of V, As, Cr, Se, Zn, and Cd exceeded considerably their dry deposition fluxes while dry deposition dominated the removal of pollution elements such as Mo, Cu, Ni, Mn, and Al. The summed dry deposition flux was four times higher than the summed wet deposition flux. Prediction results based on a simple accumulation model found that the content of seven toxic elements (Cr, Ni, Cu, Zn, As, Cd, and Pb) in soils could increase rapidly due to the impact of annual atmospheric deposition, and the increasing amounts of them reached 0.063, 0.012, 0.026, 0.459, 0.076, 0.004, and 0.145 mg kg^?1, respectively. In addition, the annual increasing rates ranged from 0.05% (Cr and Ni) to 2.08% (Cd). It was also predicted that atmospheric deposition induced the accumulation of Cr and Cd in surface soils. Cd was the critical element with the greatest potential ecological risk among all the elements in atmospheric deposition.     

Cloudwater studies at a high elevation site in the Vosges Mountains (France)

Cloud and rainwater samples have been collected at a high elevation site in the Vosges Mountains. An automated collection system has been used to collect bulk cloudwater and small cloudwater droplets. Bulk cloudwater concentrations were up to 10 times more concentrated than rainwater concentrations. Small clouddroplets showed generally higher concentrations than bulk cloudwater. Nevertheless, the enrichment factors depend on the compounds under study and appear to be related to the composition of the cloud condensation nuclei forming small or large clouddroplets. Principal component analysis and factor analysis were applied to the collected datasets and confirmed the influence of the cloud condensation nuclei on the composition difference between small and large cloudwater droplets.     

Comparisons of particulate-bound mercury (PBM) compositions in soil and vegetation at a traffic site

This investigation analyzes the particulate-bound mercury (PBM) compositions in soil and vegetation at a traffic sampling site in Taichung, Taiwan, during a sampling period from October to December, 2015. A direct mercury analyzer (DMA-80) was used to measure the particulate-bound mercury (PBM). A T-test was conducted to determine the mean differences between the PBM composition in soil and that in vegetation at the site. The results indicate that 1) the mean particulate-bound mercury compositions in soil and vegetation were the lowest in November, when the (mean OR average) wind speed was the highest (4.1 m/s); 2) Particulate-bound mercury compositions (PBM) in both soil and vegetation correlated weakly with temperature, humidity and wind speed; 3) T-test statistical results denoted that the PBM compositions did not significantly differ between soil and vegetation in the three-month sampling period.     

Polychlorinated dibenzofuran (PCDF) and dibenzo-p-dioxin (PCDD) levels in organisms and sediments from the frierfjord, southern Norway

The contamination of a fjord region by PCDD and PCDF produced from a Mg-production plant has been studied. Levels in organisms (fish, crustacea, mussels) and sediments were determined. The results allowed an estimate of the spreading of PCDD/PCDF by coastal currents. The present situation is compared with available information from other contaminated areas and with data for other contaminants in the recipient area such as hexachlorobenzene and octachlorostyrene.     

Effect of the fine fraction of particulate matter versus the coarse mass and other pollutants on daily mortality in Santiago, Chile

Daily counts of non-accidental deaths in Santiago, Chile, from 1988 to 1996 were regressed on six air pollutants--fine particles (PM2.5), coarse particles (PM10-2.5), CO, SO2, NO2, and O3. Controlling for seasonal and meteorological conditions was done using three different models--a generalized linear model, a generalized additive model, and a generalized additive model on previously filtered data. Single- and two-pollutant models were tested for lags of 1-5 days and the average of the previous 2-5 days. The increase in mortality associated with the mean levels of air pollution varied from 4 to 11%, depending on the pollutants and the way season of the year was considered. The results were not sensitive to the modeling approaches, but different effects for warmer and colder months were found. Fine particles were more important than coarse particles in the whole year and in winter, but not in summer. NO2 and CO were also significantly associated with daily mortality, as was O3 in the warmer months. No consistent effect was observed for SO2. Given particle composition in Santiago, these results suggest that combustion-generated pollutants, especially from motor vehicles, may be associated with increased mortality. Temperature was closely associated with mortality. High temperatures led to deaths on the same day, while low temperatures lead to deaths from 1 to 4 days later.     

Modelling of an enhanced PAH attenuation experiment and associated biogeochemical changes at a former gasworks site in southern Germany

Former manufactured gas plant sites often form a widespread contaminant source in the subsurface, leading to large plumes that contain a wide variety of tar-oil related compounds. Although most of these compounds eventually degrade naturally, the relevant processes tend to be slow and inefficient, often leaving active remediation as the only viable option to eliminate the risks of toxic substances to reach potential receptors such as surface waters or drinking water wells. In this study we use a reactive transport model to analyse the fate of a contaminant plume containing acenaphthene, methylbenzofurans and dimethylbenzofurans (i) prior to the installation of an active remediation scheme and (ii) for an enhanced remediation experiment during which O(2) and H(2)O(2) were added to the contaminated groundwater through a recirculation well. The numerical model developed for this study considers the primary contaminant degradation reactions (i.e., microbially mediated redox reactions) as well as secondary and competing mineral precipitation/dissolution reactions that affect the site's hydrochemistry and/or contaminant fate. The model was calibrated using a variety of constraints to test the uncertainty on model predictions resulting from the undocumented presence of reductants such as pyrite. The results highlight the important role of reactive transport modelling for the development of a comprehensive process understanding.     

Perennial observations of molecular hydrogen (H2) at a suburban site in Switzerland

Semi-continuous measurements of atmospheric molecular hydrogen $({\mathrm{H}}_2)$ and carbon monoxide (CO) were performed at a suburban sampling site in Switzerland from November 2002 to February 2005. The presented data provide information about time series, seasonal and diurnal cycles as well as sources and sinks in a suburban environment. Such records become increasingly important for the assessment of the effects of a possible future hydrogen economy on the environment. No significant trend of background ${\mathrm{H}}_2$ concentrations could be observed for the considered period. Seasonal cycles show the expected pattern with maxima in winter and minima in summer and autumn. When extracting the background ${\mathrm{H}}_2$ mixing ratios, the absolute levels as well as the seasonal amplitude agree well with literature data from semi-rural and remote sites. The ${\mathrm{H}}_2$ dry deposition velocity for summer days with low winds is estimated to be between $0.5\times {10}^{-4}$ to $1\times {10}^{-4}\mathrm{m}{\mathrm{s}}^{-1}$. Diurnal cycles are dominated by ${\mathrm{H}}_2$ emissions from nearby traffic. The influence of traffic-related emissions is also corroborated by a high ${\mathrm{H}}_2$ to CO correlation. Typical molar ${\mathrm{H}}_2$ to CO ratios from traffic were found to be 0.33 on a molar basis (ppb/ppb). A reduction of 37–62% in European anthropogenic ${\mathrm{H}}_2$ emissions is estimated for a period covering the last 25 years. Since the ambient ${\mathrm{H}}_2$ concentration did not decline during the same period, other simultaneous changes of sinks or sources of ${\mathrm{H}}_2$ must have compensated this reduction.     

Levels and composition of atmospheric particulates (PM10) in a mining-industrial site in the city of Lavrion,Greece

The present work focuses on the characterization of air quality and the identification of pollutant origin at a former mining site in the city of Lavrion, Greece. A historical metallurgy complex is reused for establishing the Lavrion Technology and Cultural Park (LTCP). A serious problem with this is the severe soil contamination that resulted from intensive mining and metallurgical activities that has taken place in the greater area for the past 3,000 years. Among other consequences, surface-polluted depositions, rich in heavy and toxic metals, are loose and easily wind-eroded, resulting in transportation of particulate matter (PM) in the surrounding atmosphere. On the other hand, there are a number of industries relatively close to the site that are potential sources of PM air pollution. The current study deals with the collection and analysis of PM10 samples with respect to their concentration in heavy metals, such as Pb, Cd, Cu, Fe, Zn, Mn, Cr, and Ni. Though not a heavy metal, As also is included. Furthermore, the source of these elements is verified using statistical correlation and by calculating enrichment factors (EFs), considering that some substances are certainly of contaminated soil origin. Results show that PM10 and element concentrations are relatively low during winter but significantly increase during summer. Fe, Pb, Zn, Mn, and Cu may be considered of contaminated soil origin, while As, Ni, Cd, and Cr are very much enriched with respect to contaminated soil, indicating another possible source attributed to the adjacent industrial plants.     

Bioavailability of PAHs in the Biobio river (Chile): MFO activity and biliary fluorescence in juvenile Oncorhynchus mykiss.

Cytochrome P450-dependent monooxygenase (MFO) activity and levels of bile PAH metabolites were measured in fish (Oncorhynchus mykiss) exposed to Biobio river (Chile) water. Experiments were performed simultaneously in both the field and laboratory to investigate whether the river water contained notable bioavailable PAH fractions. The field experiment was conducted using fish caged for 41 days at La Mochita (Biobio river mouth) whereas the laboratory experiment involved a 21-day exposure treatment with water collected in the same area. Induction of hepatic MFO, assayed by benzo(a)pyrene monooxygenase activity (BaPMO), and levels of PAH metabolites in the bile were measured in groups of eight (field experiment) and four specimens (laboratory experiment) sampled after 5, 10, 21 and 41 days of exposure. BaPMO was induced by a factor of 23 and 25 in fish caged for 21 and 41 days, respectively. Likewise, a significant BaPMO induction was found in the fish group experimentally exposed to river water for 21 days. Biliary fluorescence measurements, recorded by fixed wavelength fluorescence (FF) and synchronous fluorescence spectroscopy (SFS), revealed significantly high levels of PAH metabolites in bile samples of fish caged for 21 and 41 days. A positive relationship was found between BaPMO activity and biliary PAH metabolites. This study provides evidences that (i) Biobio river water contains a significant bioavailable PAH fraction in terms of marked effects on fish and (ii) the biological indicators MFO activity and bile PAH metabolites represent an excellent screening methodology to assess PAH exposure.     

Cadmium-induced toxicity reversal by zinc in Ceratophyllum demersum L. (a free floating aquatic macrophyte) together with exogenous supplements of amino- and organic acids

This paper analyzes the detoxification mechanisms adopted by amino- and organic acids to alleviate Cd toxicity. In addition, with our published data on Zn–Cd interactions, the influence of Zn (200 μM) supplements on the detoxification mechanisms of amino- and organic acids have also been studied. The experimental studies on metal uptake, lipid peroxidation levels, estimation of reduced and oxidized glutathione levels as well as γ-glutamylcysteine synthetase activity in amino acid supplemented Cd treatments indicated glutathione-mediated detoxification system, which was also enhanced by Zn (200 μM) supplements. However Zn did not aid in glutathione synthesis, but maintained the ratio of reduced and oxidized forms. The supplementation of organic acids to Cd treatments indicated detoxification through the mechanism of chelation. Zn seemed to be less influential on organic acids-mediated detoxification mechanism as compared to amino acid mediated detoxification system.     

Cadmium-induced toxicity reversal by zinc in Ceratophyllum demersum L. (a free floating aquatic macrophyte) together with exogenous supplements of amino- and organic acids

This paper analyzes the detoxification mechanisms adopted by amino- and organic acids to alleviate Cd toxicity. In addition, with our published data on Zn–Cd interactions, the influence of Zn (200 μM) supplements on the detoxification mechanisms of amino- and organic acids have also been studied. The experimental studies on metal uptake, lipid peroxidation levels, estimation of reduced and oxidized glutathione levels as well as γ-glutamylcysteine synthetase activity in amino acid supplemented Cd treatments indicated glutathione-mediated detoxification system, which was also enhanced by Zn (200 μM) supplements. However Zn did not aid in glutathione synthesis, but maintained the ratio of reduced and oxidized forms. The supplementation of organic acids to Cd treatments indicated detoxification through the mechanism of chelation. Zn seemed to be less influential on organic acids-mediated detoxification mechanism as compared to amino acid mediated detoxification system.     

Measurement of atmospheric fluxes of radionuclides at a UK site using both direct (rain) and indirect (soils) methods

Direct measurements of radionuclide tracers are useful tools for correcting proxy fluxes that are subject to post depositional changes. An analytical methodology was designed for the measurement of ²¹⁰Pb and ⁷Be in rainwater. Atmospheric inputs of the radionuclides to Cumbria (UK) were recorded. Rainwater fluxes were then compared with measurements from soil cores. The annual deposition from April 1997 to March 1998 of ²¹⁰Pb and ⁷Be was 165 ± 8 Bq m^-2 and 3912 ± 120 Bq m^-2, respectively, compared to an indirect ²¹⁰Pb flux of 148 ± 7 Bq m^-2 yr^-1 calculated from soil core records.     

北方滨海人工湿地水生生物群落重建效果评估——以天津临港湿地二期生态重建工程为例

为准确评估滨海人工湿地生态重建成效,科学指导工程改进方案,以重建近1年的天津临港湿地二期生态重建工程为例,通过调查重建前(2020年)和重建后(2021年)湿地水生生物群落组成变化,评价湿地生物群落重建效果。结果表明：经过近1年的生态重建,鱼类群落和底栖动物群落均得到不同程度恢复;鱼类的种类由重建前的未检出增加到10种,除泥鳅、梭鱼等增殖先锋物种未得以恢复外,其他增殖鱼类均长势良好;随着物理生境改善和先锋物种的直接投加,底栖动物数量由重建前的11种提高到重建后的28种,生物多样性明显提高;在类群组成上,底栖动物群落以自然恢复的摇蚊幼虫为主,人工投放的大型底栖物种恢复进程相对缓慢;鱼类增殖放流加剧了对浮游动物的捕食压力,造成浮游动物生物量降低和个体减小,进而导致浮游植物群落的快速响应和结构变化。基于上述研究结果,提出了水生生物群落重建优化调控建议。本研究成果可为北方滨海人工湿地重建提供借鉴。     

Transport and fate of organic wastes in groundwater at the Stringfellow hazardous waste disposal site, southern California

In January 1999, wastewater influent and effluent from the pretreatment plant at the Stringfellow hazardous waste disposal site were sampled along with groundwater at six locations along the groundwater contaminant plume. The objectives of this sampling and study were to identify at the compound class level the unidentified 40-60% of wastewater organic contaminants, and to determine what organic compound classes were being removed by the wastewater pretreatment plant, and what organic compound classes persisted during subsurface waste migration. The unidentified organic wastes are primarily chlorinated aromatic sulfonic acids derived from wastes from DDT manufacture. Trace amounts of EDTA and NTA organic complexing agents were discovered along with carboxylate metabolites of the common alkylphenolpolyethoxylate plasticizers and nonionic surfactants. The wastewater pretreatment plant removed most of the aromatic chlorinated sulfonic acids that have hydrophobic neutral properties, but the p-chlorobenzene-sulfonic acid which is the primary waste constituent passed through the pretreatment plant and was discharged in the treated wastewaters transported to an industrial sewer. During migration in groundwater, p-chlorobenzenesulfonic acid is removed by natural remediation processes. Wastewater organic contaminants have decreased 3- to 45-fold in the groundwater from 1985 to 1999 as a result of site remediation and natural remediation processes. The chlorinated aromatic sulfonic acids with hydrophobic neutral properties persist and have migrated into groundwater that underlies the adjacent residential community.