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.     

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.     

Status of industrial fluoride pollution and its diverse adverse health effects in man and domestic animals in India

Hydrofluorosis in humans and domestic animals is a worldwide health problem and caused by a prolonged period of fluoride exposure through drinking of fluoride contaminated water. But in recent years, due to rapid industrialization in India, diverse serious health problems among industrial workers and residents and domestic animals living in the industrial areas due to fluoride pollution are on the rise. A number of coal-burning and industrial activities such as power-generating stations, welding operations and the manufacturing or production of steel, iron, aluminum, zinc, phosphorus, chemical fertilizers, bricks, glass, plastic, cement, and hydrofluoric acid are generally discharging fluoride in both gaseous and particulate/dust forms into surrounding environments which create a industrial fluoride pollution and are an important cause of occupational exposure to fluoride in several countries including India. An industrial emitted fluoride contaminates not only surrounding soil, air, and water but also vegetation, crops and many other biotic communities on which man and animals are generally dependants for food. Long- time of inhalation or ingestion of industrial fluoride also causes serious health problems in the forms of industrial and neighborhood fluorosis. In India, whatever research works conducted so far on the chronic industrial fluoride intoxication or poisoning (industrial and neighborhood fluorosis) in man and various species of domestic animals due to a prolonged period of industrial fluoride exposure or pollution (contamination) are critically reviewed in the present communication. Simultaneously, we are also focused the various bio-indicators and bio-markers for chronic industrial fluoride intoxication or pollution.     

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.     

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.     

A Study of Cooling Pond Fog Generation

Airborne particulate and soil materials sampled in the vicinity of a lead/zinc smelter and subsequently digested In nitric-perchloric acids have been analyzed using an inductively coupled plasma-atomic emission spectrometer (ICP/AES). The samples were collected in two communities; a study community situated immediately adjacent to the smelter complex and a control community some 50 kilometers distant. Enrichment of airborne as well as soil materials is discussed and there is evidence of lead, zinc, copper, cadmium, arsenic, and antimony enrichment from the smelting processes. In addition, an aqueous extraction of the airborne materials isolated sulfate, nitrate, fluoride, and ammonia and gave evidence of enrichment due to fugitive SO _x , NO _x , HF, and NH₃ gaseous emissions.     

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.     

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.     

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.     

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.     

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.     

Study on fluoride emission from soils at high temperature related to brick-making process

Characteristics of fluoride emission from 12 soils at temperatures of 400-1,100 degrees C related to the brick-making process were studied. The results obtained in this study indicate that fluoride emission as gaseous HF and SiF4 was related to the firing temperature, soil total fluoride content, soil composition and calcium compounds added to soils. Soils began to release fluoride at temperatures between 500 and 700 degrees C. Marked increases of the average fluoride mission rate from 57.2% to 85.4% of soil total fluoride were noticed as the heating temperature was increased from 700 to 1,100 degrees C. It was found that the major proportion (over 50%) of the soil total fluoride was emitted from soils at approximate 800 degrees C. The amount of fluoride released into the atmosphere when heated depended on the total fluoride contents in the soils. Correlation analysis showed that the soil composition, such as cation exchange capacity, exchangeable calcium and CaCO3, had some influence on fluoride emission below 900 degrees C, but had no influence at temperatures above 900 degrees C. Addition of four calcium compounds (CaO, CaCO3, Ca(OH)2, and CaSO4) at 1.5% by weight raised the temperature at which fluoride began to be released to 700 degrees C. The greatest decrease in fluoride emission among the four calcium compound treatments was found with CaCO3.     

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.     

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 Aerosol Composition and Concentration as a Function of Particle Size and of Time

As a step toward better understanding the reactive Los Angeles air basin atmosphere, a study was undertaken at the University of California—Riverside Campus, to determine the composition and concentration of atmospheric particulate matter as a function of particle size and time. The study involved developing a method for obtaining size-classified, time-fractionated aerosol samples amenable to chemical and physical (including microscopic) analysis. During a 15-day period, samples were obtained over 4-hr periods and subsequently analyzed for nitrate, sulfate, iron, and lead. Concentration of six gaseous pollutantsj total aerosol light-scattering, and several meteorological measurements were simultaneously recorded and averaged over the 4-hr intervals. This data was presented graphically to show the diurnal variation in and relationship between gaseous, particulate, and meteorological measurements. A strong relationship between gaseous peroxyacetyl nitrate, particulate nitrate, and aerosol light-scattering was found. High concentrations of ammonium nitrate particles, mainly in the 0.5-2μ, diameter size range, were found in the atmospheric particulate samples collected on days of very high smog (very limited visibility).     

The assessment of particulate matter emitted from stone-crushing industry by correlating rock textures with particles generated after comminution and dispersed in air environment

The generation and emission of particulate matter from abrasion industry are subjects of the pollution monitoring by multidisciplinary study involving earth sciences and engineering disciplines. This work investigates the correlation between textural properties of in situ rock with class size distribution and morphology of particles generated after rock comminution and particles emitted in the air. A special comminution-dust sampling architecture was realised. The combined use of scanning electron microscopy and particle size analyser was considered in performing digital image analysis on both crushed products and airborne particles collected onto membrane filters. The results show that the size and morphology of crushed particles are linked to the petrographic rock properties. In particular, particles with fibrous morphology are prominent in rocks showing foliated textures where elongated minerals occurred, with implication for asbestos-bearing rocks. For what concerns the airborne particles, the results show that their aerodynamic diameters are independent of the crusher operating conditions. External parameters probably intervene in the distribution of the airborne particles emission, including the dynamic air fluxes, or environmental conditions. By applying mathematical models, the morphology and size range of airborne particles following the comminution processes can be predicted, and results has implication for pollutants contamination due to particulate matters emitted by crush stone industry.     

氟石膏中氟的分布及固氟脱酸改性

以工业副产物氟石膏为研究对象,通过筛分进行粒度分析,得到不同粒径pH值、水溶性氟以及总氟含量的变化规律;重点研究了掺入2种碱性工业副产物作为改性剂对氟石膏化学改性固氟脱酸的效果,从而确定改性剂的最佳掺量。结果表明,氟石膏中氟的分布有一定规律;掺加5%的电厂干法脱硫灰或2%钢铁厂烧结烟气脱硫灰能很好的起到固氟脱酸的效果。     

Seasonal and diurnal variability in airborne mold from an indoor residential environment in northern New York

It is well known that characterization of airborne bioaerosols in indoor environments is a challenge because of inherent irregularity in concentrations, which are influenced by many environmental factors. The primary aim of this study was to quantify the day-to-day variability of airborne fungal levels in a single residential environment over multiple seasons. Indoor air quality practitioners must recognize the inherent variability in airborne bio-aerosol measurements during data analysis of mold investigations. Changes in airborne fungi due to varying season and day is important to recognize when considering health impacts of these contaminants and when establishing effective controls. Using an Andersen N6 impactor, indoor and outdoor bioaerosol samples were collected on malt extract agar plates for 18 weekdays and 19 weekdays in winter and summer, respectively. Interday and intraday variability for the bioaerosols were determined for each sampler. Average fungal concentrations were 26 times higher during the summer months. Day-to-day fungal samples showed a relatively high inconsistency suggesting airborne fungal levels are very episodic and are influenced by several environmental factors. Summer bio-aerosol variability ranged from 7 to 36% and winter variability from 24 to 212%; these should be incorporated into results of indoor mold investigations. The second objective was to observe the relationship between biological and nonbiological particulate matter (PM). No correlation was observed between biological and nonbiological PM. Six side-by-side particulate samplers collected coarse PM (PM10) and fine PM (PM2.5) levels in both seasons. PM2.5 particulate concentrations were found to be statistically higher during summer months. Interday variability observed during this study suggests that indoor air quality practitioners must adjust their exposure assessment strategies to reflect the temporal variability in bioaerosol concentrations.     

Emissions from Burning Grass Stubble and Straw

The emissions from burning the residue following grass-seed harvest were determined by means of a combined laboratory-field study. Samples of the straw and stubble residue were burned in the laboratory burning tower at the University of California at Riverside. Complete analyses were determined for gaseous and particulate emissions for the important grass species from the Willamette Valley of Oregon. Particulate emissions averaged 15.6 lb/ton of fuel burned. Carbon monoxide averaged 101 lb/ton of fuel burned. Hydrocarbon emission averages, in pounds per ton of fuel burned, were 1.74 for saturates plus acetylene, 2.80 for defines, and 1.68 for ethylene. The NO_x emission, at the temperature peak during the burn, averaged 29.3 ppm. Field studies, conducted by personnel from Oregon State University, measured only particulate emissions, carbon dioxide, and temperature over the burn. The carbon dioxide values were found to be similar to those obtained on the burning table at UCR and it was therefore concluded that the other gaseous emissions were similar and could be used as reasonably accurate for emission inventories. The temperature values obtained in the laboratory and field were also similar and further justifies extrapolating the burning table data to field situations. The particulate matter collected in the field studies averaged 15.55 lb of particulate per ton of fuel burned. This is the same average obtained for the burning table data which again serves to validate the emissions reported from Riverside. Much more variability was found in the particulate emissions obtained in the field which reflects the wider range of environmental conditions encountered in the field.