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.     

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.     

Three-dimensional analytical models suitable for gaseous and particulate pollutant transport,diffusion, transformation and removal

Atmospheric diffusion models for particulate and gaseous pollutants emitted from an elevated continuous point source have been developed. The models are analytical and obtained from the solutions of steady state three-dimensional atmospheric transport-diffusion equations associated with the primary pollutant and with the secondary pollutant converted chemically from the primary pollutant. The surface dry deposition and the gravitational settling are taken into account in the models. The conversion of gaseous species to paniculate pollutant, the role of settling velocity and the effects of dry deposition velocity of gaseous species on the paniculate pollutant are analyzed.     

Fluoride Cycling near A Coastal Emission Source

A strategy of research combining intense field monitoring and compartment modeling was used to characterize fluoride cycling in the semi-arid area around a newly installed aluminum factory in southern Argentina. The factory started operations In 1974 and emitted about 500 tons of gaseous fluorides to the atmosphere up to October 1976. Emphasis of research was on sedimentary or detritus cycling; periodically, samples were obtained from plant tissues, soils, sea water, and sea sediments. A compartment model of fluoride circulation at the atmosphere-vegetation interface provides further elements to Interpret the tendencies observed in field data. A fluoride budget up to October 1976 is presented showing the relative importance of environmental compartments monitored, with reference to fluoride accumulation. Plants are transient accumulators of atmospheric fluorides; soils, sea-water, and sea-sediments are sinks of the cycle. The major pathway of fluoride from terrestrial environment to coastal sea water Is along transportation with superficial soil eroded by wind. According to data here presented, it can be concluded that one wind storm can transport enough soluble fluorides to coastal waters to account for the transient differences of concentration observed.     

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。     

Atmospheric phase distribution of oxidized and reduced nitrogen at a forest ecosystem research site

Atmospheric concentrations of gaseous NH3 and HNO3 and of particulate NH4+ and NO3- were measured during various seasons at a forest ecosystem research site in the "Fichtelgebirge" mountains in Central Europe. Air masses arriving at this site were highly variable with respect to trace compound concentration levels and their concentration ratios. However, the distributions of NH4+ and NO3- within the aerosol particle size spectra exhibited some very consistent patterns, with the former dominating the fine particle concentrations, and the latter dominating the coarse particles range, respectively. Overall, the particulate phase (NH4+ + NO3-) dominated the atmospheric nitrogen budget (particulate and gas phase, NH4+ + NO3- + NH3 + HNO3) by more than 90% of the median total mixing ratio in winter, and by more than 60% in summer. The phase partitioning varied significantly between the winter and summer seasons, with higher relative importance of the gaseous species during summer, when air temperatures were higher and relative humidities lower as compared to the winter season. Reduced nitrogen dominated over oxidized nitrogen, indicating the prevailing influence of emissions from agricultural activity as compared to traffic emissions at this mountainous site. A model has been successfully applied in order to test the hypothesis of thermodynamic equilibrium between the particulate and gas phases.     

Consideration of Air Quality Standards for Vegetation With Respect to Ozone

Present evidence suggests that ozone is the most damaging of all air pollutants affecting vegetation. It is the principal oxidant in the photochemical smog complex. Concentrations of ozone have exceeded 0.5 part per million (ppm) in the Los Angeles area. One-tenth of this level for 8 hours is known to injure very sensitive tobacco varieties. Many plant species are visibly affected after a few hours exposure at concentrations much lower than 0.5 ppm. There is also some evidence that ozone reduces plant growth. Many factors must be taken into account when considering standards to protect vegetation from ozone damage. These include ozone concentration and methods of measurement, time of exposure, possible additive effects of other pollutants, sensitivity of plant species, their economic value, and the extent of injury which can be tolerated. The response of a species to the pollutant is conditioned by genetic factors and environmental conditions. Lack of specific routine methods for measuring ozone in ambient air is a handicap. California and Colorado established standards for oxidants at 0.15 and 0.10 ppm, respectively, for 1 hour. How these standards relate to the ozone dosage causing acute and chronic injury to various plant species is discussed.     

The Effect of Rapid Transit on San Francisco Bay Air Quality

Classical procedures for the microdetermination of fluoride in vegetation are extremely time consuming. They generally involve ashing, fusion with alkali, distillation, and finally fluoride estimation. Sample size requirements for such procedures are on the order of a gram or more, making the procedure useless for determining low fluoride concentrations in small samples. A procedure for micro-fluoride determination in vegetation is proposed which utilizes the oxygen flask combustion technique (Schoniger flask). The gaseous products of combustion are absorbed in 10.0 ml of 0.05N sodium hydroxide containing 1.00 µg of fluoride. The analysis of the fluoride is performed directly on the absorption solution after addition of a combination complexing-buffer solution, using a specific fluoride ion electrode. The sensitivity of the electrode is such that 0.2 µg of fluoride can be easily detected in this volume. Added oxidant was required in the combustion step for some vegetation samples to completely free the fluoride from its organic matrix. Comparisons with the standard Willard-Winter procedure gave excellent results. Combustion of sodium fluoride standards as well as submicrogram quantities of a fluoro-organic compound showed recoveries greater than 90%. The direct combustion, coupled with fluoride ion electrode determination, reduces analysis time drastically. A complete analysis can be performed in 1/2 hr, with a minimum amount of equipment.     

BIOLEFF: three databases on air pollution effects on vegetation

Three databases on air pollution effects on vegetation were developed by storing bibliographic and abstract data for technical literature on the subject in a free-form database program, 'askSam'. Approximately 4 000 journal articles have been computerized in three separate database files: BIOLEFF, LICHENS and METALS. BIOLEFF includes over 2 800 articles on the effects of approximately 25 gaseous and particulate pollutants on over 2 000 species of vascular plants. LICHENS includes almost 400 papers on the effects of gaseous and heavy metal pollutants on over 735 species of lichens and mosses. METALS includes over 465 papers on the effects of heavy metals on over 830 species of vascular plants. The combined databases include articles from about 375 different journals spanning 1905 to the present. Picea abies and Phaseolus vulgaris are the most studied vascular plants in BIOLEFF, while Hypogymnia physodes is the most studied lichen species in LICHENS. Ozone and sulfur dioxide are the most studied gaseous pollutants with about two thirds of the records in BIOLEFF. The combined size of the databases is now about 5.5 megabytes.     

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.     

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.     

Long-term investigation of atmospheric mercury contamination in Connecticut.

Atmospheric mercury was monitored from January 1997 through the end of December 1999 in eight sampling locations in Connecticut. Four sampling locations were chosen along the shores of Long Island Sound and four were chosen in interior sections of Connecticut. Sampling locations were chosen to represent both rural and urban sectors. Average concentrations of gaseous and particulate mercury were found to be 2.06 ng/m3 and 10.5 pg/m3, respectively. The weekly average wet deposition fluxes of mercury and methylmercury over the three-year sampling period were measured to be 611 and 11 microg/ha/week, respectively. Concentrations of gaseous, particulate and wet flux of mercury were found to be significantly higher in urban areas than the rural sampling locations. There was, however, no significant difference between the mean gaseous and particulate concentrations of mercury in coastal and inland sampling locations. No significant difference was observed either between the wet fluxes of total mercury in coastal and inland sampling locations and there was no spatial gradient for mercury concentration and deposition. The data of this study suggest that vehicular traffic and localized emission sources in urban areas play a significant role in determining the atmospheric concentration of mercury in Connecticut.     

Manual Procedures for the Estimation of Atmospheric Fluorides

Manual methods for the determination of air-borne fluorides, including the discrimination of gaseous and particulate forms, have been reviewed. Published methods have been re-examined and comparative sampling data presented, to point out advantages of some newer techniques in sampling, separation, and quantitation.     

Native plant species suitable as bioindicators and biomonitors for airborne fluoride

For 30-40 years airborne fluoride, usually in the form of HF or SiF4, was one of the most important and damaging air pollutants affecting forests, crops and natural vegetation. It is much more toxic than most other air pollutants such as O3 or SO2 because injury to the most sensitive species begins when they are exposed to a concentration below 1 ppb (ca. 0.8 microg m(-3)) for a 1- to 3-day period. The long-term threshold concentration is around 0.25-0.30 microg m(-3). Higher concentrations and longer durations of exposure induce much more rapid and extensive injury. However, there is a difference in sensitivity between the most and least sensitive species of around 2-3 orders of magnitude and most species possess a degree of resistance. Dramatic improvements in engineering technology have greatly reduced emissions but because of the high toxicity, cases of vegetation injury are still common, even in developed countries, and cases involving litigation still occur. Therefore there is a continuing need for bioindicators and biomonitoring of fluorides, so this paper reviews the subject, drawing attention to the strengths and limitations of the techniques. Visible symptoms are described and illustrated and tables of relative sensitivity are given and their limitations discussed. Finally, examples of biomonitoring in Europe and the USA are presented.     

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.     

Uptake of PAHs by cabbage root and leaf in vegetable plots near a large coking manufacturer and associations with PAHs in cabbage core

Samples of ambient air (including gaseous and particulate phases), dust fall, surface soil, rhizosphere soil, core (edible part), outer leaf, and root of cabbage from eight vegetable plots near a large coking manufacturer were collected during the harvest period. Concentrations, compositions, and distributions of parent PAHs in different samples were determined. Our results indicated that most of the parent PAHs in air occurred in the gaseous phase, dominated by low molecular weight (LMW) species with two to three rings. Specific isomeric ratios and principal component analysis were employed to preliminarily identify the local sources of parent PAHs emitted. The main emission sources of parent PAHs could be apportioned as a mixture of coal combustion, coking production, and traffic tailing gas. PAH components with two to four rings were prevailing in dust fall, surface soil, and rhizosphere soil. Concentrations of PAHs in surface soil exhibited a significant positive correlation with topsoil TOC fractions. Compositional profiles in outer leaf and core of cabbage, dominated by LMW species, were similar to those in the local air. Overall, the order of parent PAH concentration in cabbage was outer leaf > root > core. Partial correlation analysis and multivariate linear stepwise regression revealed that PAH concentrations in cabbage core were closely associated with PAHs present both in root and in outer leaf, namely, affected by adsorption, then absorption, and translocation of PAHs from rhizosphere soil and ambient air, respectively.     

Factors determining amounts of fluoride in woodlice Oniscus asellus and Porcellio scaber, litter and soil near an aluminium reduction plant

Amounts of fluoride were measured in whole woodlice Oniscus asellus and Porcellio scaber, together with associated soil and litter, from 17 sites near an aluminium reduction plant at Holyhead, Anglesey, in North Wales. There was a strong positive correlation between amounts of fluoride in woodlice, soil and litter in all comparisons (P<0.02). Highest and lowest fluoride concentrations in woodlice differed by a factor of >50. Where both woodlice species occurred together at the more polluted sites, fluoride levels in Oniscus asellus were generally twice as high as those found in Porcellio scaber. At any given site, amounts of environmental fluoride were determined partly by distance and direction from the pot-rooms of the plant (a function of prevailing winds), modified by the presence of trees which acted as collectors for gaseous and particulate fluoride.     

Direct damage to vegetation caused by acid rain and polluted cloud: definition of critical levels for forest trees

The concept of critical levels was developed in order to define short-term and long-term average concentrations of gaseous pollutants above which plants may be damaged. Although the usual way in which pollutants in precipitation (wet deposition) influence vegetation is by affecting soil processes, plant foliage exposed to fog and cloud, which often contain much greater concentrations of pollutant ions than rain, may be damaged directly. The idea of a critical level has been extended to define concentrations of pollutants in wet deposition above which direct damage to plants is likely. Concentrations of acidity and sulphate measured in mountain and coastal cloud are summarised. Vegetation at risk of injury is identified as montane forest growing close to the cloud base, where ion concentrations are highest. The direct effects of acidic precipitation on trees are reviewed, based on experimental exposure of plants to simulated acidic rain, fog or mist. Although most experiments have reported results in terms of pH (H(+) concentration), the accompanying anion is important, with sulphate being more damaging than nitrate. Both conifers and broadleaved tree seedlings showing subtle changes in the structural characteristics of leaf surfaces after exposure to mist or rain at or about pH 3.5, or sulphate concentration of 150 micromol litre(-1). Visible lesions on leaf surfaces occur at around pH 3 (500 micromol litre(-1) sulphate), broadleaved species tending to be more sensitive than conifers. Effects on photosynthesis and water relations, and interactions with other stresses (e.g. frost), have usually been observed only for treatments which have also caused visible injury to the leaf surface. Few experiments on the direct effects of polluted cloud have been conducted under field conditions with mature trees, which unlike seedlings in controlled conditions, may suffer a growth reduction in the absence of visible injury. Although leaching of cations (Ca(2+), Mg(2+), K(+)) is stimulated by acidic precipitation, amounts leached are small compared with root uptake, unless soils have been impoverished. This aspect of the potential effects of acidic precipitation is best considered in terms of the long-term critical-load of pollutants to the soil. Given the practical difficulties in monitoring cloud water composition, a method for defining critical levels is proposed, which uses climatological average data to identify the duration and frequency of hill cloud, and combines this information with measured or modelled concentrations of particulate sulphate in the atmosphere, to derive cloud water concentrations as a function of cloud liquid water content. For forests within 100 m of the cloud base the critical levels of particulate sulphate, corresponding to solution concentrations in the range 150-500 micromol litre(-1), are in the range 1-3.3 microg S m(-3). These concentrations are observed over much of central Europe, suggesting that many montane forests are at risk of direct effects of fossil-fuel-derived pollutants in cloud.     

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.     

Vegetation: A Sink for Atmospheric Pollutants

The possibility of vegetation being an important sink for gaseous air pollutants was investigated. Plant pollutant uptake measurements were made utilizing a typical vegetation canopy and chambers that were designed specifically for gaseous exchange studies. The data indicate that an alfalfa canopy removed gases from the atmosphere in the following order: hydrogen fluoride (HF) > sulfur dioxide (SO₂) > chlorine (Cl₂) > nitrogen dioxide (NO₂) > ozone (O₃) > peroxyacetyl nitrate (PAN) > nitric oxide (NO) > carbon monoxide (CO). The absorption rate of NO was low, and no absorption of CO could be detected with the methods used. In the typical ambient concentration range uptake increased linearly with increasing concentration except for O₃ and Cl₂ which caused partial stomatal closure at the higher concentrations. Wind velocity above the plants, height of the canopy, and light intensity were shown to affect the pollutant removal rate. A relationship between the absorption rate and solubility of the pollutant in water was also shown. It was concluded that vegetation may be an important sink for many gaseous air pollutants.