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.     

Effects of fluorine emission on agricultural products surrounding an aluminum factory

The F concentrations of precipitate dust, agricultural products, and fingernail and hair at the surrounding Al factory were investigated. The F content of dust ranged from 15400 to 42500 micrograms/g dry weight, 190,000 to 380,000 micrograms/g Al. Rice grain contained about 3.4 times more F than that in the control area, but some kinds of agricultural products, egg plants (S. melongena L.), mulberry plants (M. japonica Bailey non Sieb.), and soy beans (G. max (L.) Merrill) were almost equal to that of controls. Also, the high F concentration in the hair and nails of some workers was affected by available F contents in the emission from the factory as well as food and water surrounding the aluminum factory compared with those of control area.     

Fluoride in mandibles and antlers of roe and red deer from different areas of England and Scotland

Fluoride concentrations were measured in mandibles of 112 male roe deer (Capreolus capreolus) aged 1-6 years, from 5 localities in England and Scotland; also in bone from sections cut in series from orbit to antler-top of 10 other roe deer. Fluoride concentrations in mandibles were mostly within values expected from unpolluted areas, but approached those expected from moderately polluted areas at the upper end of their range, which extended from 43 to 901 microg g(-1). There were large variations in mandibular fluoride content between individual animals within each age group, and an upward trend of fluoride content with increasing age. There were also considerable differences in mandibular fluoride content between localities. No gradient in fluoride concentration was evident between the upper part of the skull and various points along the antler in 9 roe deer. A tenth animal showed an increase of 65% in fluoride concentration between the skull and the top of the antler, with exceptionally high values ranging from 1220 to 2010 micro g(-1). For 3 red deer (Cervus elaphus), no significant differences in fluoride concentrations were found between trabecular and cortical antler bone.     

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.     

Stabilization of FGD gypsum for its disposal in landfills using amorphous aluminium oxide as a fluoride retention additive

The applicability of amorphous aluminium oxide as a fluoride retention additive to flue gas desulphurisation (FGD) gypsum was studied as a way of stabilizing this by-product for its disposal in landfills. Using a batch method the sorption behaviour of amorphous aluminium oxide was evaluated at the pH (about 6.5) and background electrolyte conditions (high chloride and sulphate concentrations) found in FGD gypsum leachates. It was found that fluoride sorption on amorphous aluminium oxide was a very fast process with equilibrium attained within the first half an hour of interaction. The sorption process was well described by the Langmuir model, offering a maximum fluoride sorption capacity of 61.7 mg g(-1). Fluoride sorption was unaffected by chloride co-existing ions, while slightly decreased (about 20%) by competing sulphate ions. The use of amorphous aluminium oxide in the stabilization of FGD gypsum proved to greatly decreased its fluoride leachable content (in the range 5-75% for amorphous aluminium oxide doses of 0.1-2%, as determined by the European standard EN 12457-4 [EN-12457-4 Characterization of waste-leaching-compliance test for leaching of granular waste materials and sludges-Part 4: one stage batch test at a liquid to solid ratio of 10 l/kg for materials with particle size below 10mm (without or with size reduction)]), assuring the characterization of this by-product as a waste acceptable at landfills of non-hazardous wastes according to the Council Decision 2003/33/EC [Council Decision 2003/33/EC of 19 December 2002. Establishing criteria and procedures for the acceptance of waste at landfills pursuant to Article 16 of and Annex II to Directive 1999/31/EC] on landfill of wastes. Furthermore, as derived from column leaching studies, the proposed stabilization system proved to be highly effective in simulated conditions of disposal, displaying a fluoride leaching reduction value about 81% for an amorphous aluminium oxide added amount of 2%.     

Response of Tomato Fruiting to Hydrogen Fluoride as Influenced by Calcium Nutrition

Two varieties of tomatoes grown at 40 to 200 ppm calcium were continuously fumigated with HF throughout flowering and fruit development. Fruit size was directly related to the level of calcium nutrition, and within each calcium treatment the fruits on plants subjected to HF at about 6 μg F/m³ were smaller than those on unfumigated plants. The smaller fruit size was associated with partial or complete seedlessness, suggesting that calcium plays an essential role in fertilization with which fluoride may interfere. Fluoride injury to the tomato foliage was most severe at the lowest calcium level. Treatment with HF at about 8 μg F/m³ produced some injury to tomato foliage but had no apparent effect on fruiting. Evidently fluoride can affect plant fruiting, but considering the severity of the HF treatments required, effects on tomato fruiting probably are of little practical significance. The relationship between fluoride injury and calcium nutrition suggests interference with calcium metabolism as a mechanism of fluoride injury to plants.     

Mg/Al/Fe复合氧化物吸附去除水体中氟化物的研究

采用水热法合成了不同铁掺杂量的Mg/Al/Fe型类水滑石(MAF),根据X射线衍射(XRD)的测定结果,铁存在一个最佳投加量,铁的掺杂量过大则会导致水滑石的层状结构被破坏。通过扫描电镜(SEM)和比表面分析仪(BET)研究了MAF焙烧后的复合金属氧化物(CMAF)的结构和性能,并考察了CMAF对水中氟离子的吸附性能。与CMA相比(铁掺杂量为零),CMAF对氟离子的吸附去除效率明显提高(最大吸附容量75.2 mg/g),整个吸附过程可以用Langmuir吸附等温线更好地描述。通过XRD测定和晶格参数计算,CMAF的结构由吸附前的复合氧化物恢复到层状水滑石结构,表明氟离子在水滑石重构过程中作为层间阴离子进入到水滑石内部,从而达到较高的除氟效率。     

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.     

Removal of hexafluoroarsenate from waters

Arsenic predominantly occurs in natural ground and surface waters as arsenate and arsenite. Other arsenic species can also be present in anthropogenically influenced waters. By means of a newly-developed speciation technique an arsenic compound was identified as hexafluoroarsenate at high concentration (about 0.8mgl(-1) as As) in a lake polluted by waste water from a former crystal glass factory. This compound shows a completely different behavior than common arsenite and arsenate in waters. However, respective literature data were little found regarding its environmental behavior as well as the applicable remediation technologies. Conventional arsenic treatment mechanisms, such as the well-known sorption to iron hydroxides, can not be used to remediate water with this compound. Hence, an effective method to remove hexafluoroarsenate from water was developed using its strong affinity to anion exchangers (strong basic exchangers with quaternary ammonium groups). The sorption can be described by a Langmuir isotherm and first-order kinetics with a half-life of about 10min. Interferences by sulphate and fluoride, present at much higher concentrations in the polluted lake water, might be expected due to the anion exchange mechanism, but were shown to be of minor importance.     

化学-混凝沉淀处理含氟含重金属废水研究

为解决某铝材电镀工业园含氟含重金属废水达标排放的问题,研究了化学混凝沉淀法同时处理该废水中氟与金属的效果及影响因素,采用正交和单因素实验确定了最佳工艺条件。结果表明,当CaCl₂投加量与废水中氟离子摩尔比为5∶1（即CaCl_{质量4 782 mg/L）,聚氯化铝（PAC）用量为500 mg/L,pH为9.5,聚丙烯酰胺（PAM）用量2 mg/L时,出水中残留F离子浓度可降至8 mg/L,Cu²⁺、Ni²⁺、Cr⁶⁺和Zn²⁺出水浓度分别降至0.05、0.07、0.3和0.1 mg/L,出水能达到《水污染物排放限值》（DB44/26-2001）第二时段一级标准,且最为经济。}     

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 in the prey of barn owls (Tyto alba)

Bone fluoride in short-tailed voles (Microtus agrestis) and common shrews (Sorex araneus), the prey of barn owls (Tyto alba), was studied on Anglesey, North Wales. The average fluoride content of M. agrestis skulls obtained from a location 0.9 km from an aluminium reduction plant was significantly greater than that of skulls from another location 22 km from the source of industrial fluoride pollution. At both locations, mean fluoride levels of skulls extracted from owl pellets and those of voles trapped mechanically were broadly similar but important differences existed. Near the aluminium reduction plant, owls caught voles and shrews with a much wider range of fluoride levels than occurred at a single trapping site. However, there was no evidence for selection of heavily fluoridated prey. Within 1 km of the aluminium reduction plant, six trapping sites yielded S. araneus with a fourfold difference between the highest and lowest mean bone fluoride level.     

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.     

Atmospheric deposition of fluoride in the lower Tamar Valley,Tasmania

Soluble fluoride (F⁻), measured using an ion-selective electrode, was monitored during 1982–1983 in monthly bulk (wet and dry) atmospheric deposition samples collected at 17 locations in the lower Tamar Valley, Tasmania, where an aluminium (Al) smelter is located. Glass samplers (funnel-bottle type) were used, with duplications by plastic samplers at five locations later. The spatial and temporal variations in F⁻ deposition in relation to wind flow and rainfall are discussed, and its impact on the environment is highlighted. The mean deposition rates of F⁻, as measured from September 1982 to August 1983, ranged from about 90 μg m⁻² day⁻¹ at the intended ‘background’ location to 12,568 μg m⁻²day⁻¹ at a location about 1 km east-southeast from the smelter. The depositional fluxes of F⁻ and insoluble Al (another elemental tracer of the smelter) are significantly correlated (P < 0.001). They were much higher within 3 km of the smelter, where vegetation damage by fluoride contamination was most evident. However, air emissions from the smelter could travel at least 10 km up the valley. Wet deposition was the predominant removal process for F⁻ during autumn and winter, while dry deposition appeared to be more significant in summer. The plastic samplers collected about 8 and 17% more F⁻ and Al, respectively, but with higher standard deviations. Thus the variations observed could be largely due to sampling fluctuations.     

活化赤泥的除氟性能

以成本低的铝工业废矿渣（赤泥）为原材料,通过高温煅烧和酸化处理对赤泥进行活化,制备了除氟吸附剂。研究了反应时间、投加量、初始氟浓度、溶液温度、共存阴离子和pH值对活化赤泥除氟效果的影响。结果表明,接触反应时间为18 h时,吸附接近平衡。活化赤泥对氟离子的吸附符合Lagergren二级吸附动力学方程。另外,初始浓度越高,吸附容量越大。与Freundlich相比,Langmuir吸附等温模型可以更好地描述氟离子的吸附特性,最大吸附量可达2.71 mg/g。SO24-、Cl-和NO3-存在时（〈1 000 mg/L）,对氟离子的吸附几乎没有影响,然而,HCO3-、PO34-和氟离子共存时,会对氟吸附造成不利影响。活化赤泥在pH值3.5～11.0时,具有较好的吸附稳定性。活化赤泥是一种吸附容量高、性能稳定的环境友好型除氟材料,具有应用潜力。     

Variations in chemical composition of birch foliage under air pollution stress and their consequences for Eriocrania miners

The relationships between chemical composition of birch foliage, individual performance and population density of both solitary and gregarious species of Eriocrania leafminers (Lepidoptera: Eriocraniidae) were studied in the vicinity of the Harjavalta copper-nickel smelter, southwestern Finland. The contents of heavy metals (Cu, Ni, Fe and Zn) in birch foliage exponentially decreased with the distance from the factory whereas the content of manganese showed the opposite trend. Performance parameters of Eriocrania miners were correlated neither with the distance from the pollution source nor with the foliar content of heavy metals. However, larval masses of both solitary and gregarious species were highest at the zone of moderate pollution. The levels of total nitrogen and total carbon and the carbon: nitrogen ratio in birch leaves showed no clear patterns in relation to distance from the factory. Feeding efficiency of solitary larvae increased with higher foliar nitrogen content but decreased when the carbon: nitrogen ratio was high. Survival of solitary Eriocrania species was negatively correlated with total leaf carbon content. However, the population density of solitary miners showed a negative correlation with total foliar nitrogen and a positive correlation with the carbon:nitrogen ratio. Performance of the gregarious E. haworthi was not correlated with the chemical composition of birch leaves, whereas population density was highest close to the factory complex and correlated positively with the levels of copper and nickel in birch leaves. Consequently, pollution-induced changes in measured host plant chemicals were unlikely to affect population densities of Eriocrania miners via altered larval performance.     

Temporal variation of fluoride concentration in antlers of roe deer (Capreolus capreolus) living in an area exposed to emissions from iron and steel industry, 1948-2000

Temporal changes of environmental fluoride concentration in the industrialized area of Siegen, western Germany were assessed by studying the fluoride content of antlers (n=116) collected between 1948 and 2000 from the resident roe deer (Capreolus capreolus) population. During the analyzed period, major fluoride emission sources in the study area have been iron- and steelworks. Fluoride concentrations in the antlers ranged between 118 and 5428 mg/kg of bone ash. There was an overall increase in antler fluoride content from the late 1940s/early 1950s to the late 1950s/mid-1960s. Thereafter, antler fluoride levels overall steadily declined. For statistical analysis, the data were grouped into five periods (1948–1959, 1960–1969, 1970–1979, 1980–1989, and 1990–2000). Geometric mean fluoride concentrations of the samples ranged from 323 (period 1990–2000) to 2096 mg/kg of bone ash (period 1960–1969). Sample means for the periods 1980–1989 and 1990–2000, respectively, were always significantly lower than those of older samples. The decrease in antler fluoride concentrations during recent decades suggests a drop of ambient fluoride levels, that is hypothetically attributed to a reduction in the number of emission sources in the area and a decline of fluoride discharges from both local and more distant sources due to improved emission control measures. Comparison with antler fluoride data for other roe deer populations from western Germany further suggests that the roe deer from the Siegen area were recently exposed to an only moderate additional fluoride load from industrial sources. Studying antler fluoride concentrations is a convenient and cost-effective method of monitoring temporal changes in ambient fluoride levels.     

Fluoride loading of a lepidopteran larva (Pieris brassicae) fed on treated diets

Experiments to assess the impact of dietary fluoride on larvae of Pieris brassicae were designed to substantiate field observations that at polluted sites little fluoride is absorbed by insect larvae and that most of the body load is caused by surface contamination. Treatment with fluoride as HF or AlF3 had no effect on pupal weight of Pieris and we conclude that fluoride, at concentrations likely to be found on vegetation at polluted sites, is unlikely to have a direct impact on the growth of chewing herbivores. Fluoride in the gut formed the biggest component of the total body load. A significant amount of fluoride was detected in exuviae, but resulted from surface contamination. When larvae from polluted food were transferred to untreated food it took several days for the fluoride content of the faeces to return to background levels.     

Exposure to polychlorinated biphenyls in residents near a chemical factory in Italy: the food chain as main source of contamination

High levels of PCBs were recently found in soil, food and some farmers living close to a chemical factory which until the 1980s had produced polychlorinated biphenyls (PCBs) in Brescia, North Italy. We performed a survey on a random sample of subjects aged 20-79 years living in various areas of the town with different levels of soil pollution to investigate factors associated with increased levels of PCB in serum (24 congeners were tested). Total PCB values were closely related to age (Spearman r=0.68; p<0.0001). The 166 consumers of locally produced food had higher PCB levels than non-consumers (median=1143 versus 719; 95th centile=9301 versus 2635ng/g lipid) with the highest levels among consumers of food produced in the most contaminated area close to the factory (median=2551; 95th centile=33464ng/g lipid). A dose-effect relationship between consumption of food produced in this area and PCB blood levels was observed (Spearman r=0.52, p=0.0014). Consumers of only plant food produced in this area had higher levels of PCB than non-consumers (median=1100; 95th centile=10,800ng/g lipid). Three subjects who had worked at the factory in the past showed high PCB levels. Distribution of PCB congeners did not differ between consumers of locally produced food and non-consumers, apart from PCB 209 which was found at high levels in former factory workers and was more common among consumers of food produced in the polluted area. In conclusion, we found high serum PCB levels in humans living in a highly polluted area in an industrialized town in Italy, due mainly to consumption of food produced in polluted areas.     

春蚕期桑叶氟化物含量变化规律分析与研究

春蚕桑叶氟化物中毒引起政府部门的高度重视。通过对历年来桑叶含氟量监测数据统计分析，找出春蚕期桑叶含氟量日均值变化规律，并对规律成因进行探讨研究，为春蚕防氟工作提供科学依据。