Environmental monitoring of fluoride emissions using precipitation, dust, plant and soil samples

A pollution gradient was observed in precipitation, plants and soils sampled at different locations around a fluoride producing chemical plant in Germany. In all samples the influence of emissions was discernible up to a distance of 500 m from the plant. However, fluoride concentrations in plant bioindicators (leaves of birch and black berry) and in bulk precipitation showed a more pronounced relationship with the distance from the source than fluoride concentrations in soil. Vegetables sampled in the vicinity of the plant also had elevated concentrations of fluoride, but only the consumption of larger quantities of this material would lead to exceedances of recommended daily F-intake. The present study did not indicate the existence of low phytotoxicity thresholds for fluoride in the plant species used in the study. Even at very high fluoride concentrations in leaf tissue (963 ppm) plants did not show injury due to HF. Dust sampling downwind of the chemical plant confirmed that particulate fluoride was of minor importance in the study area.     

Effects of airborne fluoride emissions near an aluminium works in Wales: part 2--saxicolous lichens growing on rocks and walls

Effects of fluoride (F(-)) emissions on previously unpolluted assemblages of saxicolous lichens, near an aluminium reduction works, are described. Lichens contained a mean 16 microg F(-) g(-1) dry weight in 1970 before emissions commenced. Subsequently, where annually monitored Ramalina contained >100microg g(-1) severe damage occurred, including loss of attachment to the rocky substratum. At sites within 1 km of the works well-exposed to emissions, fruticose (shrubby) lichens were eliminated, but in more sheltered locations 18% cover had survived by 1983. Some foliose (leaf-like) lichens tolerated >200 microg g(-1), while crustose (crust-like) species were least affected, 32% and 70% surviving, respectively. Concentrations of fluoride, and associated injury, decreased with increasing distance from the works. Fruticose and sensitive foliose species sustained 40-75% losses of cover up to 4 km NE, downwind of the works, where fluoride averaged 50-100 microg g(-1), but <40% losses were recorded in fruticose species up to 9 km, where concentrations averaged 35-50 microg. Saxicolous lichens were damaged less than corticolous species previously reported and, following decreased emissions, were also regrowing in sheltered and more distant locations by 1985.     

Effects of airborne fluoride emissions near an aluminium works in Wales: part 1-corticolous lichens growing on broadleaved trees

Effects of emissions, from a new aluminium works, on previously unpolluted assemblages of corticolous lichens, are described. Injury symptoms included chlorosis, red colorations, necrosis and weakening of attachment of thalli to the bark substratum, resulting in reductions in % cover. Before emissions commenced in 1970, lichens contained <10microg fluoride (F(-)) g(-1) dry weight. Where concentrations in annually monitored samples of Ramalina reached >100microg F(-1) g(-1), within 4 km downwind of the works, severe injury occurred with >75% losses of cover of some species. At increasing distances, injury, and F(-) concentrations, decreased. The lichen flora was almost eliminated within 1 km of the works: after 15 years' operation, 37 species are absent within 650 m, but at least 43 survive at 900 m. A range of sensitivity was shown between, and within, morphological types. Fructicose (shrubby) lichens contained >600microg F(-1) g(-1) after 4 years and were the first, and most severely, affected (<1% cover surviving by 1975). Most foliose (leaf-like) species were sensitive (88% losses by 1977), but some were more tolerant, containing >400microg F(-1) g(-1) after 10 years. Crustose (crust-like) lichens were affected least, some growing markedly to occupy the space formed following elimination of more intolerant species. Since 1978, in response to decreasing emissions, there has been a recovery of some fruticose and foliose species in less-exposed locations.     

Spatio-temporal behaviour and mass balance of fluorine in forest soils near an aluminium smelting plant: short- and long-term aspects

With the help of a large number of monitoring sites, the behaviour of F in forested ecosystems of a formerly polluted area (M?hlin and Rheinfelden, Switzerland) could be studied over 30 years. An aluminium smelting plant originated the pollution of this area in the past: however, after the installation of a filtration plant in 1958 the F emissions were reduced and since 1991 almost absent the primary production of aluminium was stopped. The present-day area with elevated F contents (water-soluble F with >20 mg/kg) is restricted to a radius of about 1000 m from the plant. In 1969 this area had a radius of about 3 and 5 km. Between 1969 and 2000 a significant decrease in the soluble F content in the soil was observed together with a substantial decrease of F in the vegetation. The net losses of water-soluble F in the soil were in the range of 35 up to more than 70% of the original concentration and the F losses in the vegetation between 60 up to more than 80%. After the reduction of high F deposition rates the accumulated SOM was decomposed within the observation period 1969-1993. The combined decrease in F and humus led to chain reactions with losses of major elements and a dealumination of clay minerals, i.e. removal of interlayered Al of 2:1 minerals and consequent formation of smectites.     

Linkage of biomarkers along levels of biological complexity in juvenile and adult diazinon fed terrestrial isopod (Porcellio scaber, Isopoda, Crustacea)

In parallel laboratory experiments, we determined the effect of a typical representative of organophosphorous pesticides, diazinon, on AChE activity, lipid, protein and glycogen content, weight change, feeding activity and mortality of juvenile and adult terrestrial isopods Porcellio scaber (Isopoda, Crustacea). Organophosphorous pesticides (OP) are among the most extensively used pesticides, which have replaced organochlorine pesticides. OPs inhibit the enzyme acetylcholinesterase (AChE), resulting in neurotoxicity. They have more widespread effects on non-target organisms than do organochlorine pesticides. The aim of this study was to link effect of diazinon on target enzyme to energy reserves and to integrated biomarker responses in juvenile and adult P. scaber. The non-observed effect concentration (NOEC) for AChE activity after diazinon exposure in two weeks toxicity study with isopods was below 5 microg/g diazinon. There was a good agreement between concentrations at which AChE and survival were affected (10 microg/g diazinon in juveniles, 100 microg/g diazinon in adults). We revealed a link among AChE activity, protein content and mortality. Glycogen and lipid content, feeding activity and weight change were not affected in two weeks diazinon exposure up to 100 microg/g diazinon. Juveniles were affected at concentrations that were an order of magnitude lower than those provoking similar effects on adults. Recommendations are made for future toxicity studies with terrestrial isopods.     

Effect of compost and manure amendments on zinc soil speciation, plant content, and translocation in an artificially contaminated soil

The addition of organic matter in soil can modify the bioavailability of heavy metals. A greenhouse pot experiment was carried out using an edible plant species Eruca vesicaria L. Cavalieri grown on an artificially contaminated soil with Zn (665 mg?kg^?1). In this study, the effect of compost at 20 t?ha^?1 (C20) and at 60 t?ha^?1 (C60), manure at 10 t?ha^?1 (M10) and at 30 t?ha^?1 (M30), and chemical fertilizers (NPK) on Zn fate in a soil–plant system was evaluated. At the end of the experiment, the main growth parameters and Zn content in plants were determined. In addition, Zn speciation in the soil was assessed using the original Community Bureau of Reference sequential extraction and diethylene triamine pentaacetic acid extraction. Zinc, though an essential element for plant growth, caused toxicity effects in plants grown on control and manure treatments, while in the compost treatments, plants showed no visual toxicity symptoms. The concentrations of Zn in roots were similar for all treatments, while significant differences were observed for shoots. In fact, in the compost treatments, plants showed the lowest Zn concentration in shoots. Zinc speciation seems not to be affected by the applied treatments. Indeed, Zn plant content and translocation to shoots seems to be affected. Compost amendments significantly reduced Zn content and translocation in comparison to other treatments.     

Micro-spatial variation of soil metal pollution and plant recruitment near a copper smelter in Central Chile

Soil chemical changes produced by metal smelters have mainly been studied on a large scale. In terms of plant survival, determination of small scale variability may be more important because less toxic microhabitats may represent safe sites for successful recruitment and thus for plant survival. Three dominant microhabitats (open spaces and areas below the canopy of Sphaeralcea obtusiloba and Baccharis linearis shrubs) were defined in a heavily polluted area near a copper smelter and characterised in terms of microclimate, general soil chemistry, total and extractable metal concentrations in the soil profile (A0 horizon, 0-5 and 15-20 cm depth), and seedling densities. Results indicated a strong variability in microclimate and soil chemistry not only in the soil profile but also among microhabitats. Air/soil temperatures, radiation and wind speed were much lower under the canopy of shrubs, particularly during the plant growth season. Soil acidification was detected on top layers (0-5 cm depth) of all microhabitats while higher concentrations of N, Cu and Cd were detected on litter and top soil layers below shrubs when compared to open spaces; however, high organic matter content below shrubs decreased bioavailability of metals. Plant recruitment was concentrated under shrub canopies; this may be explained as a result of the nursery effect exerted by shrubs in terms of providing a more favourable microclimate, along with better soil conditions in terms of macronutrients and metal bioavailability.     

An application of parametric and nonparametric models to the assessment of fluoride levels in vegetation exposed to stack emissions of an aluminum reduction plant in Greece

Various statistical models were developed for assessing airborne fluoride (F) levels in natural vegetation near an aluminum reduction plant using as predictor variables the distance from the emission source, the predominating wind, and characteristic topography-geomorphology parameters. Results revealed that F concentrations in vegetation showed a predictable response to both wind conditions and landscape features. The linear model was found to give good estimations, taking advantage of the relatively strong linear correlation between concentration and distance. A nonlinear relationship between the F concentration in vegetation and the other variables was also found, while interactions between the variables were found to be non-first-order. The nonlinear relationship hypothesis was supported by the improved results of various nonlinear models that also indicated the importance of the area's topography-geomorphology and meteorology in model predictions. The application of an artificial neural network (ANN) model showed the closest agreement between predicted and observed values with a correlation coefficient of 0.92. The improved reliability of the ANN and a regression tree model (RTM) also were indicated by the normal distribution of their residuals. The RTM and the ANN were further investigated and found to be capable of identifying the importance of the variables in vegetation exposure to air emissions.     

Heavy metal contamination and risk assessment in water,paddy soil,and rice around an electroplating plant

Purpose  

The objective of this paper is to assess the impact of long-term electroplating industrial activities on heavy metal contamination in agricultural soils and potential health risks for local residents.     

Leaching,mobility and persistence of tebufenozide in columns packed with forest litter and soil

Abstract

Leaching, downward mobility and persistence of tebufenozide was investigated under laboratory conditions in columns packed with forest litter and soil, after fortification with the analytical grade material (purity > 99.6%) and with two commercial formulations, RH‐5992 2F (aqueous flowable) and RH‐5992 ES (emulsion suspension). Two types of litter and soil were used: one type with relatively high amounts of sand and the other with high amounts of clay.

The concentrations eluted in the leachates were lower when the analytical material (dissolved in acetone) was used for fortification, than when the two formulations (diluted with water) were used. The amount leached was higher for RH‐5992 2F than for RH‐5992 ES. The type of substrate, i.e., sandy or clay type, had only marginal influence on the amounts eluted in the leachates. Downward movement of tebufenozide from the top 2‐cm layer to the untreated middle and bottom layers (3‐cm segments) was consistently lower when the analytical material was used for fortification, than when the two formulations were used. Downward movement was higher for RH‐5992 2F than for RH‐5992 ES. Persistence of tebufenozide in substrates, maintained under submerged conditions for 70 days after leaching, indicated an initial 2‐week lag period prior to the onset of degradation. Formulation‐related differences were observed in the half‐life (DT₅₀) values. When the analytical material was used for fortification, the DT₅₀ ranged from ca 54 to 59 d. However, when the formulations were used for fortification, the DT₅₀ showed a higher range, i.e., from ca 62 to 67 d for RH‐5992 2F and ca 70 to 80 d for RH‐5992 ES. Formulation ingredients appear to have caused enhanced adsorption of tebufenozide onto the substrates, thus delaying degradation.     

Factors determining the fluctuation of fluoride concentrations in PM10 aerosols in the urbanized coastal area of the Baltic Sea (Gdynia, Poland)

Fluoride concentrations were determined in PM10 samples collected in the urbanized coastal area of the Baltic Sea (Gdynia) in the period between 1 August 2008 and 8 January 2010. F^? concentrations remained within the range of 0.4–36.6 ng?·?m^?3. The economic transformations which have taken place in Poland increasing ecological awareness have had an excellent effect on the levels of fluoride pollution in the air of the studied region. In our measurements, fluoride concentrations increased in wintertime, when air temperature dropped, at low wind speeds (<1 m?·?s^?1) and with low dispersion of pollutants originating from local sources (traffic, industry, domestic heating). At times when wind speed grew to >10 m?·?s^?1, fluorides were related to marine aerosols or else brought from distant sources. Apart from wind speed and air temperature, other significant meteorological parameters which determined the variability of F^? turned out to be air humidity and precipitation volume. Aerosols were washed out effectively, even with small precipitation (h?=?4 mm), and if a dry period lasted for several days, their concentrations grew rapidly to over 30.0 ng?·?m^?3.     

Influence of pesticides on acetylene reduction and growth of microorganisms in an organic soil

The effects of 32 pesticides at two concentrations on acetylene reduction (non-symbiotic nitrogen fixation), nitrogen fixers, bacteria and fungi in an organic soil were assessed. None of the pesticide treatments suppressed C2H2 reduction as compared to controls. No significant inhibition of the population of non-symbiotic nitrogen fixers occurred. However, stimulatory effects were observed with treatments of fensulfothion, fonofos, oxamyl, DDR, TeloneR and Telone CR. Bacterial and fungal populations showed temporary declines but all recovered within 7 days to levels similar to or higher than those in the controls.     

Influence of pesticides on acetylene reduction and growth of microorganisms in an organic soil 1

Abstract

The effects of 32 pesticides at two concentrations on acetylene reduction (non‐symbiotic nitrogen fixation), nitrogen fixers, bacteria and fungi in an organic soil were assessed. None of the pesticide treatments suppressed C H reduction as compared to controls. No significant inhibition of the population of non‐symbiotic nitrogen fixers occurred. However, stimulatory effects were observed with treatments of fensulfothion, fonofos, oxamyl, DD^R , Telone^R and Telone C^R . Bacterial and fungal populations showed temporary declines but all recovered within 7 days to levels similar to or higher than those in the controls.     

Ambient air concentrations of polycyclic aromatic hydrocarbons,fluoride, suspended particles and particulate carbon in areas near aluminum production plants

Concentrations of airborne polycyclic aromatic hydrocarbons (PAH), fluoride, suspended particles and particulate carbon were determined in four different residential areas near aluminum industries. Two of the areas were exposed to pollutants from primary aluminum production, the third area was close to a plant manufacturing electrodes for the aluminum industry while the fourth area received pollutants from the production of aluminum as well as electrodes. The sampling time was 24 h and the samples were collected every eighth day for about 16 months. The concentrations of PAH were high compared to levels in other polluted areas with industry and dense traffic. The average concentrations for benzo(a)pyrene (BaP) were above 10 ngm⁻³, which has been proposed as a guideline in some countries, at all sites. The highest air concentration of BaP measured in the present study was 160 ng m⁻³. At two of the stations the fluoride concentrations exceeded the 24-h national guideline of 25 μgm⁻³, which has been set to protect human health. In a few cases the concentrations of suspended particles were high while the levels of carbon agreed with concentrations reported in urban and residential areas in U.S.A. The concentrations varied with time and the variation was caused mainly by the changes of the meteorological conditions. The frequency distributions were skew for all components and close to logarithmic normal. PAH were well correlated with fluoride, which is an aluminum production tracer, indicating that they are of the same origin. The aluminum industry did not seem to be the main source of particulate matter and carbon in air. Apportionment studies of the organic pollutants were carried out by cluster analysis, and the results showed that the aluminum production is the main source to the PAH in ambient air in these areas.     

Effects of plant arsenic uptake and heavy metals on arsenic distribution in an arsenic-contaminated soil

This study examined the effects of heavy metals and plant arsenic uptake on soil arsenic distribution. Chemical fractionation of an arsenic-contaminated soil spiked with 50 or 200mg kg(-1) Ni, Zn, Cd or Pb was performed before and after growing the arsenic hyperaccumulator Pteris vittata L for 8weeks using NH(4)Cl (water-soluble plus exchangeable, WE-As), NH(4)F (Al-As), NaOH (Fe-As), and H(2)SO(4) (Ca-As). Arsenic in the soil was present primarily as the recalcitrant forms with Ca-As being the dominant fraction (45%). Arsenic taken up by P. vittata was from all fractions though Ca-As contributed the most (51-71% reduction). After 8weeks of plant growth, the Al-As and Fe-As fractions were significantly (p<0.01) greater in the metal-spiked soils than the control, with changes in the WE-As fraction being significantly (p=0.007) correlated with plant arsenic removal. The plant's ability to solubilize soil arsenic from recalcitrant fractions may have enhanced its ability to hyperaccumulate arsenic.     

Interactive effects of nitrogen deposition and fire on plant and soil chemistry in an alpine heathland

The response of alpine heathland vegetation and soil chemistry to N additions of 0, 10, 20 and 50 kg N ha⁻¹ year⁻¹ in combination with simulated accidental fire (+/−) was monitored over a 5-year period. N addition caused rapid and significant increases in plant tissue N content and N:P and N:K of Calluna vulgaris, suggesting increasing phosphorus and potassium limitation of growth. Soil C:N declined significantly with N addition, indicating N saturation and increasing likelihood of N leakage. Fire further decreased soil C:N and reduced potential for sequestration of additional N. This study shows that alpine heathlands, which occupy the headwaters of many rivers, have limited potential to retain deposited N and may rapidly become N saturated, leaking N into downstream communities and surface waters.     

Dissipation of alachlor in cotton plant, soil and water and its bioaccumulation in fish

Dissipation of alachlor in soil and plant in field condition (cotton cropping system), and in soil, water and fish in simulated model ecosystem was investigated. The acetanilide herbicide, alachlor (50% w/w EC) was applied as pre-emergence at 2.5 and 5.0 kg a.i.ha(-1) three days after sowing the cotton seeds in the field. Soil and plant samples were collected at intervals and analyzed for alachlor residues. To study the fate of alachlor in water and fish, a simulated model ecosystem was constructed and fish was introduced one day after herbicide application. The dissipation of alachlor in water and soil and bioaccumulation in fish was observed in model ecosystem. At harvest, cotton lint and seed samples were found to contain alachlor well below the detectable level. However, trace amounts of residues were found in cotton oil. After harvest of cotton, coriander (Coriandrum sativum) and edible amaranth (Amaranthus mangostanus L.) were raised for herbicide bioassay. The green leafy vegetable samples did not show any toxic symptoms of alachlor residues.     

Mobility of Zn, Cd and Pb in soils as affected by poultry litter extract--I. Leaching in soil columns

Application of poultry litter to cropland may increase metal mobility, because the soluble organic ligands in poultry litter can form water-soluble complexes with metals. In this study, one uncontaminated soil and two metal-contaminated soils were sampled. A portion of the uncontaminated soil was amended with Zn, Pb, and Cd at rates of 400, 200, and 8 mg kg(-1), respectively. Packed soil columns were leached with H2O, EDTA, CaCl2, and poultry litter extract (PLE) solutions separately. No leaching of Zn, Cd, and Pb with the PLE was found in the uncontaminated soil. The retention of PLE-borne Zn indicated the potential for Zn accumulation in the soil. A large portion of the metals was leached from the metal-amended soil, and EDTA solubilized more Zn, Cd, and Pb than CaCl2 and PLE. In the metal-contaminated soils, the leaching of Zn and Cd with PLE was consistently larger than that for CaCl2, indicating that these metals were mobilized by organic ligands. The PLE did not mobilize Pb in these soils. The utilization of poultry litter in metal-contaminated soils might accelerate the movement of Zn and Cd in soil profiles.     

Atmospheric deposition of PCDD/Fs near an old municipal solid waste incinerator: levels in soil and vegetation

The levels of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) were determined in soil and vegetation samples taken from 24 sites in the vicinity of an old municipal solid waste incinerator (San Adrià del Besòs, Barcelona, Spain). Duplicate samples were collected within a radius of 3 km from the stack. PCDD/F concentrations in soils ranged from 1.22 to 34.28 ng I-TEQ/kg (d.m.) with median and mean values of 9.06 and 12.24 ng I-TEQ/kg, respectively. In turn, the levels of PCDD/Fs in vegetation samples ranged from 0.33 to 1.98 ng I-TEQ/kg (d.m.), with median and mean values of 0.58 and 0.70 ng I-TEQ/kg, respectively. Although the present PCDD/F concentrations in soil samples were higher than those recently found in soils taken near other incinerators from Catalonia, they are of the same order of magnitude than the levels of these pollutants found in incinerators from other countries. By contrast, the concentrations of PCDD/Fs in herbage samples were comparable to those found in recent surveys carried out in Catalonia.