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。     

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.     

Some Responses of Vegetation to Atmospheric Fluorides

Three investigations into the physical and chemical fate of fluorides in plants yielded immediately useful information and suggested lines of additional fruitful study. Reported here, two deal with effects of environmental conditions on fluoride uptake from the atmosphere, and a third considers a possible effect of internal fluorides on cell wall permeability.     

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.     

The Optical Evaluation of Smoke or Participate Matter Collected on Filter Paper

Many food, fiber, forage, and forest crops and a number of animals are adversely affected by a variety of air pollutants. The more important and generally occurring of these pollutants are ethylene, fluorides, ozone, peroxyacyl nitrates (PAN), and sulfur oxides. Their effects upon animals and plants can best be judged by criteria which describe the reaction of biologic materials to pollutant concentration and exposure time. Four criteria are recognized: (1) interference with enzyme systems; (2) change in cellular chemical constituents and physical structure; (3) retardation of growth and reduction in production from altered metabolism; and (4) acute immediate tissue degeneration. Information on tissue degenerative effects due to these pollutants is the most common; there are some reports on growth and productivity reduction; but little data are available on cellular alterations and interference with enzymes. Determination and measurement of the latter two criteria are essential to the ultimate definition and prediction of the significance of the effects of pollutants on growth and productivity of agriculture. Dosage data are available which indicate the degenerative effects of some specific pollutants on certain tissues of hosts. Political-social judgments can be made because of the knowledge of the effects of these specific pollutants; this knowledge thus permits the establishment of standards which define air quality necessary for the protection of agriculture. The importance of combined pollutant effects mitigates against the ready setting of standards on an airshed or significant regional basis. The setting of standards for a single polluiant effects upon crops and animals effectively serves as a precedent and indicates the necessity of establishing air quality values for pollutant mixtures emitted into and produced within the air resource at different geographic locations as the polluted air moves throughout the typically multigovernment jurisdictions of the airsheds.     

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.     

Operating Experience with the Alcoa 398 Process for Fluoride Recovery

During the 1940’s, aluminum smelting installations were increased in size to provide aluminum necessary for World War II. Increased evolution of fluorides made necessary the capture and treatment of pot gases. Following the application of water scrubbers, cyclones, and electrostatic precipitators, Alcoa Research Laboratories at New Kensington, Pa., discovered that small quantities of HF gas would react at low temperature with alumina. Following a series of design efforts, the Alcoa 398 Process was developed, incorporating a fluidizedbed reactor to contact pot gases with incoming feed alumina. Bag filters are used to separate entrained solid materials from pot gases. Ninety-five percent interception of pot gases is reported with 99% recovery of fluorides from gases treated. No significant effect is observed on purity of metal produced.

Installation costs are in the range of $>28-$37 per annual ton for new installations and about 50% more for conversion of old plants. These are somewhat less than the conventional electrostatic precipitators and water scrubbers at today’s prices. Direct operating costs for the Alcoa 398 Process range from $2.90 to $4.70/ton of aluminum and recover $8 worth of fluorine, giving a net credit. This contrasts with $3.93/ton of aluminum to operate existing precipitator scrubber combinations. The Alcoa 398 Process is being rapidly extended throughout the Alcoa system.     

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.     

Height growth of different European Scots pine Pinus sylvestris L. Provenances in a heavily polluted and a control environment

Results are presented of height measurements and degree of needle injury on five-year-old plants of Scots pine (Pinus sylvestris L.) growing near a phosphate fertiliser plant that emits SO(2) and fluorides. The populations of Scots pine represented in this experiment originate from 11 countries and were substantially differentiated in height growth and extent of needle necroses. Those populations which grew most rapidly were found to be the most sensitive to pollutant injury. The least productive provenances from the north of the range (Sweden, USSR) are at the same time characterized by lowest decline in height growth, lowest mortality and least extensive necroses. It is proposed that gene banks be established for the best genotypes likely to be eliminated in the heavily polluted conditions of Poland today.     

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 Standards for the Protection of Farm Animals from Fluorides

The ingestion of forages contaminated with inorganic fluorides from industrial sources constitutes an air pollution problem for domestic livestock. In cattle, which have been studied most extensively, the syndrome is characterized by dental and skeletal lesions, lameness, chemical evidence of increased fluoride ingestion, and in severe cases by effects on appetite and milk production. The only practical basis for a standard appears to be one based on forage fluoride concentrations. It is concluded that a standard should protect cattle from loss of milk production and from severe dental fluorosis, but need not be set so low that the animals will be protected against any discernible deviations from normal which do not influence their general health, productive ability, or the soundness and wearing quality of their dentition. As there may be wide seasonal variations in forage fluoride concentrations, the basic standard should be expressed as a yearly average of the forage fluoride concentration. However, as the developing teeth may be adversely influenced by short periods of high exposure, the standard should contain a provision which limits both the extent and duration of time that high concentrations may be tolerated even though they are balanced by lower values at other months. Based on these criteria, a tentative standard which limits forage fluoride to an average of 40 ppm, and limits the time that forage concentrations may exceed 60 or 80 ppm F is proposed.     

Canadian Activities in Ambient Air Quality Criteria and Development of Standards

Within recent years, increasing attention has been directed to the determination of contaminant levels in urban and industrial areas involving particulate matter (dustfall, suspended matter and smoke), sulfur dioxide, hydrogen sulfide, fluorides, ozone or oxidant, oxides of nitrogen and polycyclic aromatic hydrocarbons. However, with regard to criteria and evaluation of effects, none of these pollutants has been studied as thoroughly as sulfur dioxide. Presently, three provinces in Canada have adopted acts or regulations dealing with the control of air pollution. The Ontario Act, passed in 1958 and amended in 1963 and 1964, is the most comprehensive in scope. The Damage by Fumes Arbitration Act of Ontario provides for the awarding of compensation where crops, trees or other vegetation is damaged by sulfur fumes arising from the smelting or roasting of nickel-copper ore or iron ore or from the treatment of sulfides for the production of sulfur of sulfuric acid for commercial purposes. Regulations have also been enacted in Manitoba and Alberta. A provincial act is under consideration in Saskatchewan.     

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.     

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.     

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.     

Synthesis of environmentally relevant fluorinated surfactants--a review

In the past years there has been a growing interest in fluorinated persistent organic pollutants such as perfluorooctanesulfonic acid, perfluorooctanesulfonamides, perfluorinated carboxylic acids and fluorotelomer alcohols. Although these compounds have probably been present in the environment for many decades, we are only now beginning to realize that these environmental contaminants may have serious environmental and health effects. This article gives a state-of-the-art review of synthetic approaches that have been employed for the synthesis of these environmentally relevant fluorinated compounds. Perfluorooctanesulfonic acid derivatives, in particular, pose a problem because only a few perfluorooctanesulfonic acid derivatives are available from commercial sources--a fact that limits the ability of researchers worldwide to further study these compounds. Because of the limited literature available, this article also describes synthetic approaches for shorter chain homologues or perfluoroether analogues that can potentially be applied for the synthesis of perfluorooctanesulfonic acid derivatives. The preparation of typical starting materials for the synthesis of perfluorooctanesulfonic acid derivatives such as the perfluoroalkanesulfonyl fluorides and chlorides will be discussed. Subsequently, their conversion into relevant perfluoroalkane sulfonate salts (R(F)SO3M), sulfonamides (R(F)SO2NH2), N-alkyl sulfonamides (R(F)SO2NHR, R = alkyl), N,N-dialkyl sulfonamides (R(F)SO2NR2, R = alkyl), sulfonamidoethanol (R(F)SO2NRCH2CH2OH, R = -H, -CH3 or -C2H5) and sulfonamidoacetates (R(F)SO2NRCH2CO2H, R = -H, -CH3 or -C2H5) will be described. Many perfluorinated carboxylic acids and fluorotelomer alcohols are available from commercial sources. The review of the synthesis of these two classes of fluorinated compounds includes a review of their industrial synthesis and the synthesis of relevant degradation products.     

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.     

Self-purification ability of a resurgence stream

The self-purification ability of a resurgence stream has been investigated by taking samples along the course of a channeled tract made up of a first part in beaten soil (3.3 km) and a second in concrete (7.2 km). The study has been conducted by statistically processing pre-existent data, acquired monthly by analyzing waters at the beginning and at the end of the whole canal for 6 years, from 1995 to 2000 (historic data), and by performing specific experiments (recent data) to evaluate differently the self-purification capacity of the beaten soil section and that in concrete. A significant abatement of concentrations has been observed from historic data for ammonium, phosphates, turbidity, heavy metals and bacteria. From the recent data, all these parameters seem to decrease in the beaten soil tract. Whereas significant further decreases in the concrete tract were observed only for ammonium, phosphates and bacteria. For other parameters, e.g. pH, dissolved oxygen, chlorides, fluorides, sodium, and sulfates, a significant increase was observed from the historic data.     

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.     

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.