Autocorrelation and univariate time series modelling for grass fluoride and airborne fluoride concentrations

The dependence of observed fluoride levels-grass, gaseous air and particulate air-on previous levels was investigated in the field situation. Autocorrelation was found in grass fluoride observations, and to a lesser extent was present in both gaseous and particulate airborne fluorides. Univariate time series models were obtained which accounted for 56-66% of total variation in grass fluoride, 31% in gaseous airborne and 26% in particulate airborne fluorides. The large amount of variation unexplained by the models was thought to be due to the influence of environmental and meteorological factors not included in the models, and random variation due to day-to-day and plot-to-plot variation.     

Fluoride deposition in snow in the surroundings of a mixed fertilizer factory

The fluoride content of snow was determined at various distances from a mixed fertilizer factory in Siilinjärvi, central Finland. Elevated fluoride levels were observed at less than 2 km from the factory, and the highest concentrations close to the factory were about 600 μg of fluoride per liter of melt water. At unpolluted reference sites the fluoride content was about 6μg/1. The background level of fluoride in precipitation is discussed. An ion selective electrode and a simple calibration method were used in the analyses.     

环境中氟化物的迁移和转化及其生态效应

本文对环境中氟化物的迁移和转化及其对人体、动物、植物的污染生态效应作一简要的综述,主要包括以下几方面：１．环境中氟化物的来源及其地球化学特征;２．土－水－气－食物链中氟化物的迁移和积累与地方性氟流行病;３．土－水－气中氟的迁移和积累与植物氟毒效应;４．土－水－气中氟的迁移和积累与蚕桑氟化物污染;５．环境中氟污染的防治对策。     

A Study of Ozone Levels in a Maritime and Land Environment

During the summer of 1976, a comparison was made between ozone measurements for a coastal industrial concentration area (Norfolk/Virginia Beach, Virginia) and an offshore station (Chesapeake Light Station, 15 miles out to sea). The anticipated dominance of high offshore ozone readings with offshore flow was not observed. A surprising number of high O₃ concentrations were observed at both the offshore and land sites with northeasterly and easterly winds. This suggests that the phenomenon of long range transport of contaminants from highly urbanized centers in the northeast to the mid-Atlantic states via an offshore sea route must be given careful consideration. The body of information presented in this paper points out the need for a clearer understanding of the complex urban/rural O₃ problem coupled with transport effects before costly control strategies are to be implemented.     

Multivariate stochastic modelling of grass fluoride and airborne fluorides

Stochastic modelling was used to investigate the influence of airborne fluorides (in the case of grass fluoride) and meteorological factors on both grass and airborne fluoride levels, taking into consideration lagged dependence. Using rigorous grass sampling methods, there were indications of a negative relationship between volume of rainfall and grass fluoride concentrations, but no apparent relationship between the time which the leaf was visibly wet and grass fluoride levels. No evidence was found that rainfall washed airborne fluoride from the atmosphere or that wind variables influenced grass fluoride. For one particular experimental site, a multivariate stochastic model, which accounts for 81% of the total variation of the grass fluoride series, is developed.     

Redox potential characterization and soil greenhouse gas concentration across a hydrological gradient in a Gulf coast forest

Soil redox potential (Eh), concentrations of oxygen (O2) and three greenhouse gases (CO2, CH4, and N2O) were measured in the soil profile of a coastal forest at ridge, transition, and swamp across a hydrological gradient. The results delineated a distinct boundary in soil Eh and O2 concentration between the ridge and swamp with essentially no overlap between the two locations. Critical soil Eh to initiate significant CH4 production under this field conditions was about +300 mV, much higher than in the homogenous soils (about -150 mV). The strength of CH4 source to the atmosphere was strong for the swamp, minor for the transition, and negligible or even negative (consumption) for the ridge. Maximum N2O concentration in the soils was found at about Eh +250 mV, and the soil N2O emission was estimated to account for less than 4% for the ridge and transition, and almost negligible for the swamp in the cumulative global warming potential (GWP) of these three gases. The dynamic nature of this study site in response to water table fluctuations across a hydrological gradient makes it an ideal model of impact of future sea level rise to coastal ecosystems. Soil carbon (C) sequestration potential due to increasing soil water content upon sea level rise and subsidence in this coastal forest was likely limited and temporal, and at the expense of increasing soil CH4 production and emission.     

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.     

Evaluation of Probes Used for Source Sampling of Hydrogen Fluoride

The body of information presented in this paper is directed to those individuals concerned with methods for the sampling and measurement of fluorides contained in stack gases produced during the manufacture of phosphate fertilizer or aluminum. An air stream containing gaseous hydrogen fluoride (HF), at concentrations of from 87 to 1700 µg F m^-3, was generated and passed through 193 to 198 cm lengths of Pyrex glass, type 316 stainless steel, TFE Teflon, and methyl methacrylate-coated aluminum probes at flow rates of 28 I min^-1. HF passing through the probes was collected in deionized water contained in a Greenburg-Smith impinger. The Teflon probe exhibited no loss of HF and no trend toward increased passage of HF with time. Significant amounts of fluoride were lost in 18 out of 20 tests with the methacrylate probe and in 4 out of 20 tests with the Pyrex and stainless steel probes. Trends toward increased passage of HF with time occurred with the latter three probe materials. The selective ion electrode and semiautomated methods gave equivalent results when samples were made alkaline to avoid sorption of fluoride by Tygon tubing used in the semiautomated method. These results demonstrated that a Teflon probe gave the most representative sample of gaseous HF. However, additional tests are needed before a final recommendation is made for a probe to sample fluorides in stack gases.     

Air Quality Criteria for the Effects of Fluorides On Man

Minute traces of fluoride are found in the air of rural communities and of cities, having been contributed perhaps from volcanic effluvia, perhaps from burning coal, and perhaps from industrial sources. Atmospheres of urban areas of the U. S. have been found to contain from less than 0.2 μg F/m³ to as much as 1.9/μg F/m³. Fluorides released from industrial processes may release elemental fluorine, soluble gaseous fluorides, and soluble or insoluble fluoride dusts. At least in some instances inhaled fluoride from fluoride containing dusts has proven to be as biologically available as that from similar concentrations of inhaled HF. Measurement of the amount of fluoride excreted in the urine has proven to be a valuable index of exposure and a means of preventing cumulative injury. Average urinary F concentrations not exceeding 5 mg/liter, which corresponds approximately to a daily intake of 5 mg, are not associated with osteosclerosis in such workmen, and such changes are unlikely at daily intakes of 5 – 8 mg F. The amount of fluoride which is retained by an individual inhaling air containing 2.5 mg of fluoride dusts per m³ (the current TLV) is approximately 5-6 mg. A review of the literature describing the exposure of work forces to fluorides in industrial atmospheres indicates that concentrations have ranged from a fraction of a milligram/m³ to values mostly less than 10 mg/ml Surveys of populations living near installations emitting fluoride fumes or dusts indicate that, with few exceptions, the health of these persons has not been adversely affected. Many species of vegetation are far more susceptible to the effects of fluoride than is man, hence an air quality standard to protect vegetation will be far lower than those encountered in the factory, and can be expected to be of the order of 10 ppb or less. The probable daily intake of F at this level of exposure is 0.16 mg, an intake far below that required for the production of clear-cut effects in the human. Thus, air quality standards set to protect vegetation would contribute negligible quantities of F in terms of any possible adverse effect on human health, and would give a wide margin of protection for man.     

Air Quality Standards for Fluoride Vegetation Effects

Facts that must be taken into consideration in developing fluoride standards for vegetation effects include: (1) Fluoride is an accumulative toxicant and injury is usually associated with long-term exposure; (2) gaseous and particulate fluorides differ in their phytotoxicity; (3) plant species and varieties differ greatly in susceptibility to fluoride; (4) extremely low concentrations can cause damage to sensitive species. Three possible approaches to standards are discussed: Atmospheric fluoride concentration, vegetation fluoride concentration, and the presence of leaf necrosis or chlorosis. Atmospheric fluoride concentration has the advantage that it fits the conventional concept of standards and that it is objective. Accurately measuring low fluoride concentrations, separating gaseous from particulate fluorides in the air sample, and establishing a safe concentration present technical problems, however. Vegetation analysis may more closely represent fluorides available to affect the plant. The presence of significant amounts of fluoride-induced leaf necrosis (e.g., 3% of the leaf area) may be the most practical approach to standards for fluoride vegetation effects. Advantages are that the combined effects of the forms of fluoride, species and varieties, and concentration-time relationships are all manifest in the factor that is measured. Relatively little time is required to examine the vegetation in a large area and only 2 or 3 surveys a year are required.     

Active biomonitoring of airborne fluoride near an HF producing factory using standardised grass cultures

In order to study the pollution gradient in the vicinity of an HF producing factory, a biomonitoring programme was performed employing VDI standardised grass cultures. Specimen plants of Lolium multiflorum cv. Lema were exposed at 11 sites over five monthly periods and the biomass produced was used for subsequent F-analyses. Meteorological data from the study region confirmed that wind direction accounted for changes in the pollution pattern over periods of time. Fluoride concentrations in the grass cultures, however, were unrelated to temperature and precipitation sums during the exposures. The biomass production of the grass cultures proved to be unrelated to these parameters as well but, with the enhanced growth of the plants, the fluoride concentrations were lower due to the dilution of the element with higher biomass accumulation. Because the contribution of particulate fluoride was unknown, both the washed grass cultures and the washing water were analysed in order to determine the amount of external fluoride. Washing reduced the fluoride concentrations by 22% on average, indicating that most of the element was internal fluoride stemming from stomatal uptake. Larger amounts of fluoride, however, could be washed off from grass cultures exposed at sites close to the factory indicating that dust emissions played a greater role at these locations. Because particulate emissions were supposed to arise from CaF₂ and the waste-product anhydrite, grass cultures were also analysed for calcium and sulphur. While calcium concentrations were generally high but unrelated to fluoride, sulphur concentrations showed a slight relationship to the F-concentrations determined in the unwashed plants. Latter findings indicate the co-deposition of the two elements as surface bound, external loads, but bioindication could not clarify to what extent both elements were partitioned in the gas-to-particle phase. We therefore recommend using the grass culture method in air quality programmes to identify any exceedances of European feeding stuff standards in the vicinity of large emitters.     

fluoride concentrations in the ambient air

The body of the information presented in this paper is of general interest to those concerned with air quality. This paper reports data for ambient atmospheric concentrations of water-soluble fluorides determined in samples of suspended particulate matter collected on glass-fiber filters by the National Air Surveillance Network. Data for over 12,000 samples collected in calendar years 1966, 1967, and 1968 are examined. The purpose of the examination of the data is to give an estimation of current air quality with respect to fluoride content.

The samples are extracted with pure boiling water, and the fluoride concentration of the extracts measured using a fluoride-ion selective electrode. The data engendered are tabulated on an annual basis, and a table is presented summarizing the results. Comparative data will be presented showing the distribution of urban and non-urban stations that exhibit various specified fluoride levels. The results show that the fluoride content in the majority of the samples is below the minimum detectable amount of 0.05 µgF/m³. Conclusions that can be drawn include the observations that: few of the urban samples contain over 1.00 µg/m ³ of fluoride, very few of all samples exceeded 1.00 µ/m³ of fluoride, and no non-urban sample contained over 0.16 µg/m³ of fluoride. It was also concluded that only in rare instances would the fluoride concentrations at the sites sampled be in excess of published standards.     

Fluoride cycling in nature through precipitation

Recent studies on fluoride measurement in precipitation from coastal and inland areas suggest that anthropogenic sources are the major contributors rather than preferential injection at the air-sea interface, as suggested earlier. However our studies with samples collected from marine, coastal and inland sites in the Indian subcontinent establish definite contribution of fluoride from sea salt. The correlation between F and Na follows the power law y = ax^b with similar slopes for all sites, excepting the urban sites where anthropogenic sources dominate. The study establishes a background fluoride concentration in precipitation in the range of 1–12 ppb, with a mean around 5 ppb.     

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.     

Flow rates of ions in waters percolating through a model ecosystem with forest trees

From 1983-88 the long-term effects of low level exposure with O(3), SO(2) and simulated acid rain on mineral cycling in model ecosystems with spruce, fir and beech seedlings were investigated. Systems consisting of open-top chambers built above lysimeters were protected against the intrusion of ambient rain and dust. As part of the investigations on mineral cycling the fluxes of elements with water input and output of the canopy and soil compartments are presented. During the 5 year duration of the experiment, pronounced effects on canopy deposition and cation leaching were observed. Most noticeable were throughfall enrichment with sulfate through dry deposition of SO(2) as influenced by duration of needlewetting and factors promoting SO(2) oxidation. Depending on sulfur deposition, leaching of calcium, magnesium, manganese, zinc and ammonium from canopies was elevated, in total leading to enhanced soil input of acid. After 15 months, the water percolating the soils in the lysimeters of these treatments was acidified, with elevated flowrates of sulfate, manganese, calcium and magnesium. The results on canopy/soil leaching are compared to those from old conifer stands in the field.     

Distribution of chromium, cadmium, nickel and lead in agricultural soils collected from Kazanli-Mersin, Turkey

This study reports total levels of chromium, cadmium, nickel and lead in the agricultural land adjacent a factory producing chromate compounds in Kazanli-Mersin. Surface soil samples were collected from fields around the factory as well as from fields farther away to measure contamination due to aerial transportation and deposition of dust produced in the industrial process. Heavy metals in soil were extracted using wet digestion, and concentrations were measured by atomic absorption spectrophotometry. The concentrations were compared with Turkish maximum allowable concentration values. The metal concentrations averaged 80, 0.14, 228 and 431mg1kg^-1 for chromium, cadmium, nickel and lead, respectively. Soil samples contaminated with chromium were mainly found 500–20001m from the factory and decreased with increasing distance from the factory. Elevated chromium and nickel concentrations were determined in the soils around the factory, especially to the northwest (prevailing wind) and west. Lead concentrations exceeded the limit in only roadside soils (4000 and 50001m to the west), but tended to increase in the vicinity of industrial activity (especially in the west, the northwest and the north). The cadmium concentration did not exceed the limit and was within the normal range for soils.     

BETR North America: a regionally segmented multimedia contaminant fate model for North America

We present the Berkeley-Trent North American contaminant fate model (BETR North America), a regionally segmented multimedia contaminant fate model based on the fugacity concept. The model is built on a framework that links contaminant fate models of individual regions, and is generally applicable to large, spatially heterogeneous areas. The North American environment is modeled as 24 ecological regions, within each region contaminant fate is described using a 7 compartment multimedia fugacity model including a vertically segmented atmosphere, freshwater, freshwater sediment, soil, coastal water and vegetation compartments. Inter-regional transport of contaminants in the atmosphere, freshwater and coastal water is described using a database of hydrological and meteorological data compiled with Geographical Information Systems (GIS) techniques. Steady-state and dynamic solutions to the 168 mass balance equations that make up the linked model for North America are discussed, and an illustrative case study of toxaphene transport from the southern United States to the Great Lakes Basin is presented. Regionally segmented models such as BETR North America can provide a critical link between evaluative models of long-range transport potential and contaminant concentrations observed in remote regions. The continent-scale mass balance calculated by the model provides a sound basis for evaluating long-range transport potential of organic pollutants, and formulation of continent-scale management and regulatory strategies for chemicals.     

Eutrophication of freshwater and coastal marine ecosystems a global problem

GOAL, SCOPE AND BACKGROUND: Humans now strongly influence almost every major aquatic ecosystem, and their activities have dramatically altered the fluxes of growth-limiting nutrients from the landscape to receiving waters. Unfortunately, these nutrient inputs have had profound negative effects upon the quality of surface waters worldwide. This review examines how eutrophication influences the biomass and species composition of algae in both freshwater and costal marine systems. MAIN FEATURES: An overview of recent advances in algae-related eutrophication research is presented. In freshwater systems, a summary is presented for lakes and reservoirs; streams and rivers; and wetlands. A brief summary is also presented for estuarine and coastal marine ecosystems. RESULTS: Eutrophication causes predictable increases in the biomass of algae in lakes and reservoirs; streams and rivers; wetlands; and coastal marine ecosystems. As in lakes, the response of suspended algae in large rivers to changes in nutrient loading may be hysteretic in some cases. The inhibitory effects of high concentrations of inorganic suspended solids on algal growth, which can be very evident in many reservoirs receiving high inputs of suspended soils, also potentially may occur in turbid rivers. Consistent and predictable eutrophication-caused increases in cyanobacterial dominance of phytoplankton have been reported worldwide for natural lakes, and similar trends are reported here both for phytoplankton in turbid reservoirs, and for suspended algae in a large river CONCLUSIONS: A remarkable unity is evident in the global response of algal biomass to nitrogen and phosphorus availability in lakes and reservoirs; wetlands; streams and rivers; and coastal marine waters. The species composition of algal communities inhabiting the water column appears to respond similarly to nutrient loading, whether in lakes, reservoirs, or rivers. As is true of freshwater ecosystems, the recent literature suggests that coastal marine ecosystems will respond positively to nutrient loading control efforts. RECOMMENDATIONS AND OUTLOOK: Our understanding of freshwater eutrophication and its effects on algal-related water quality is strong and is advancing rapidly. However, our understanding of the effects of eutrophication on estuarine and coastal marine ecosystems is much more limited, and this gap represents an important future research need. Although coastal systems can be hydrologically complex, the biomass of marine phytoplankton nonetheless appears to respond sensitively and predictably to changes in the external supplies of nitrogen and phosphorus. These responses suggest that efforts to manage nutrient inputs to the seas will result in significant improvements in coastal zone water quality. Additional new efforts should be made to develop models that quantitatively link ecosystem-level responses to nutrient loading in both freshwater and marine systems.     

Developing a multimedia model of chemical dynamics in an urban area.

A multimedia model has been developed to account for the movement of semi-volatile organic compounds (SOCs) in an urban environment. The model, based on a Level III fugacity model of D. Mackay (Multimedia Environmental Models: The Fugacity Approach, Lewis Publishers, Boca Raton, FL, 1991), consists of six compartments: air, surface water, sediment, soil, vegetation, and an organic film that coats impervious surfaces. The latter is a newly identified compartment into which gas-phase SOCs partition and particle-phase SOCs are believed to be efficiently captured (M.L. Diamond, S.E. Gingrich, K. Fertuck, B.E. McCarry, G.A. Stern, B. Billeck, B. Grift, D. Brooker, T.D. Yager, Environ. Sci. Technol., 34 (2000a), 2900-2908). The model, parameterized for downtown Toronto, Ontario, Canada, and run with an illustrative emission rate for selected polycyclic aromatic hydrocarbons and homologues of polychlorinated dibenzodioxins, indicates that the film achieves the highest concentrations among media but that soils are the greatest sink for all but the least hydrophobic chemicals. The film "reflects" the more volatile chemicals into air, facilitates removal to surface waters by wash-off, and provides a surface on which photolytic degradation can occur. As such, the film is a transient sink that increases chemical mobility in urban areas by increasing air concentrations and the cycling of these compounds between air and urban surfaces and increasing water concentrations. Vegetation also accumulates SOCs, a portion of which is transferred to soil that reduces chemical mobility.     

Atmospheric Tracer Techniques and Gas Transport in the Primary Aluminum Industry

The results of 35 Individual SF₆ tracer tests conducted in Norway during 1978 demonstrate the applicability of tracer techniques to the study of a wide variety of pollutant transport problems found in the primary aluminum industry. Tracer methods were employed to determine the efficiency of the pollutant control system over a single reduction cell under a variety of operating conditions. Two tests conducted during normal operation gave efficiencies equal to 100 ±19% and 79 ± 12%, while a test performed during the occurrence of an anode effect yielded an efficiency equal to 66 ± 22%.

Tracer investigations of flow in the wake of a smelter hall indicated that between 1 % and 11 % of secondary, roof-top emissions can become entrained in the recirculation cavity and reenter the hall through the ventilation fresh air supply. These reentry rates were observed for release heights as high as 8 m above the existing roof exhaust duct. Tracer dispersion data collected within 20 building heights of the smelter agreed very well with extrapolations of McEIroy- Pooler dispersion curves for an urban area. Dispersion curves determined from a previous wind tunnel study of flow downwind of an isolated building underestimated dispersion downwind of the vs.melter complex.

The total fluoride mass flow rate measured downwind of a smelter during wet, foggy conditions indicated that wet removal rates of fluorides are in the range 3.2 × 10^?4/s to 6.4 × 10^?4/s. Simulation of the source with several tracer point releases and simultaneous measurement of fluoride and tracer ground-level concentrations downwind of the smelter eliminated the need for measurements of vertical profiles of wind speed and fluoride concentration during the experiment.