Total toxicity equivalents emissions of SF6, CHF3, and CCl2F2 decomposed in a RF plasma environment

Sulfur hexafluorine compound (SF6), trifluoromethane (CHF3) and diclorodifluoromethane (CCl2F2) are extensively used in the semiconductor industry. They are global warming gases. Most studies have addressed the effective decomposition of fluorine compounds, rather than the toxicity of decomposed by-products. Hence, the concepts of toxicity equivalents (TEQs) were applied in this work. The results indicated that HF and SiF4 were the two greatest contributors of TEQ to the SF6/H2/Ar plasma system, while F2 and SiF4 were the two greatest contributors to the SF6/O2/Ar system. Additionally, SiF4 and HF were the two greatest contributors of TEQ to both the CHF3/H2/Ar and CHF3/O2/Ar plasma systems. HF and HCl were the two greatest contributors of TEQ to the CCl2F2/H2/Ar plasma system, and Cl2 and COCl2 were the two greatest contributors to the CCl2F2/O2/Ar system. HCl and HF can be recovered using wet scrubbing, which reduces the toxicity of these emission gases. Consequently, the hydrogen-based plasma system was a better alternative for treating gases that contained SF6, CHF3 and CCl2F2 from the TEQs point of view.     

Abatement of sulfur hexafluoride emissions from the semiconductor manufacturing process by atmospheric-pressure plasmas

Sulfur hexafluoride (SF6) is an important gas for plasma etching processes in the semiconductor industry. SF6 intensely absorbs infrared radiation and, consequently, aggravates global warming. This study investigates SF6 abatement by nonthermal plasma technologies under atmospheric pressure. Two kinds of nonthermal plasma processes--dielectric barrier discharge (DBD) and combined plasma catalysis (CPC)--were employed and evaluated. Experimental results indicated that as much as 91% of SF6 was removed with DBDs at 20 kV of applied voltage and 150 Hz of discharge frequency for the gas stream containing 300 ppm SF6, 12% oxygen (O2), and 40% argon (Ar), with nitrogen (N2) as the carrier gas. Four additives, including Ar, O2, ethylene (C2H4), and H2O(g), are effective in enhancing SF6 abatement in the range of conditions studied. DBD achieves a higher SF6 removal efficiency than does CPC at the same operation condition. But CPC achieves a higher electrical energy utilization compared with DBD. However, poisoning of catalysts by sulfur (S)-containing species needs further investigation. SF6 is mainly converted to SOF2, SO2F4, sulfur dioxide (SO2), oxygen difluoride (OF2), and fluoride (F2). They do not cause global warming and can be captured by either wet scrubbing or adsorption. This study indicates that DBD and CPC are feasible control technologies for reducing SF6 emissions.     

Investigation of a new approach to decompose two potent greenhouse gases: photoreduction of SF(6) and SF(5)CF(3) in the presence of acetone

In this paper, we addressed the utilization of photochemical method as an innovative technology for the destruction and removal of two potent greenhouse gases, SF(6) and SF(5)CF(3). The destruction and removal efficiency (DRE) of the process was determined as a function of excitation wavelength, irradiation time, initial ratio of acetone to SF(5)X (X represented F or CF(3)), initial SF(5)X concentration, additive oxygen and water vapor concentration. A complete removal was achieved by a radiation period of 55min and 120min for SF(6)-CH(3)COCH(3) system and SF(5)CF(3)-CH(3)COCH(3) system respectively under 184.9nm irradiation. Extra addition of water vapor can enhance DRE by approximately 6% points in both systems. Further studies with GC/MS and FT-IR proved that no hazardous products such as S(2)F(10), SO(2)F(2), SOF(2), SOF(4) were generated in this process.     

Decomposition of SF6 in an RF Plasma Environment

Abstract

Sulfur hexafluoride (SF₆)-contained gas is a common pollutant emitted during the etching process used in the semiconductor industry. This study demonstrated the application of radio-frequency (RF) plasma in the decomposition of SF₆. The decomposition fraction of SF₆ [η_SF6 (C_in–C_out)/C_in x 100%] and the mole fraction profile of the products were investigated as functions of input power and feed O₂/SF₆ ratio in an SiO₂ reactor. The species detected in both SF₆/Ar and SF₆/O₂/Ar RF plasmas were SiF₄, SO₂, F₂, SO₂F₂, SOF₂, SOF₄, S₂F₁₀, S₂OF₁₀, S₂O₂F₁₀, and SF₄. The results revealed that at 40 W, η_SF6 exceeded 99%, and the reaction products were almost all converted into stable compounds such as SiF₄, SO₂, and F₂ with or without the addition of oxygen. Sulfur oxyfluorides such as SO₂F₂, SOF₂, SOF₄, S₂OF₁₀, and S₂O₂F₁₀ were produced only below 40 W. The results of this work can be used to design a plasma/chemical system for online use in a series of a manufacturing process to treat SF₆-containing exhaust gases.     

Effects of experimental parameters on NF(3) decomposition fraction in an oxygen-based RF plasma environment

Clean procedure is one of the major emitters of perfluorinated compounds (PFCs) in semiconductor manufacturing. Nitrogen trifluoride (NF(3)) is increasingly the process gas of choice for eliminating PFC emissions. However, its toxic to human and similar global warming potential compared to most other PFCs made NF(3) warranted much more investigation. This study demonstrated a radio-frequency plasma system for decomposing NF(3). The effects of experimental parameters: input power, O(2)/NF(3) ratio, operational pressure and NF(3) feeding concentration on NF(3) decomposition fraction (eta(NF3)) and energy efficiency E(NF3) were examined in detail. The analytical results demonstrated that the NF(3) was almost completely decomposed (>99%) at input power=30W, [NF(3)](in)=1.0% and eta(NF3) increased with input power. However, adding O(2) to the system inhibited NF(3) decomposition and decreased E(NF3). Moreover, eta(NF3) and E(NF3), decreased with gradually increasing operational pressure. Notably, increasing the NF(3) feeding concentration increased molecule density, reducing eta(NF3), but increasing E(NF3). Furthermore, the products detected in the NF(3)/O(2)/Ar plasma system were NO(2), NO, N(2)O, SiF(4), N(2) and F(2). Potential reaction pathways in the oxygen-based NF(3) plasma environment were built-up and elucidated.     

Kinetics of Sulfur-Oxide Formation in Flames: II. Low Pressure H2S Flames

The microstructure of 1/10 and 1/20 atmosphere, lean H₂S—O₂—N₂ flames is developed using the mass-spectrometric flame-sampling technique. The flame mechanism developed is in agreement with that determined from an earlier study on 1-atm H₂S flames. The formation of SO₂ appears to be primarily related to the production of SH and the ensuing oxidation steps SH + O₂ = SO + OH and SO + O₂ = SO₂ + O. While there is some question whether SO₂ formation occurs via an SO or an S₂O intermediate, the present study does not give direct support to the role of S₂O in the oxidation mechanism. However, the presence of significant quantities of free sulfur in the pre-flame zone may be indicative of S₂O formation via SO + S → S₂O, and, possibly, via the disproportionation of SO, 3SO → S₂O + SO₂. Kinetic analyses of some of the pre-flame reactions indicate an apparent activation energy of 17,300 calories/mole for the decomposition of H₂S. The actual initiation process in the flame mechanism requires further examination. The specific rate for the reaction step H₂S + O = OH + SH is given by k ₆ = 1.45 × 10₁₅ exp ( – 6600/RT) cm³ mole^–1 sec^–1, and the specific rate for the oxidation of SO, SO + O₂ = SO₂ + O, is given by k ₅ = 5.2 × 10₁₄ exp (—19,300/RT) cm³ mole^–1 sec^–1.     

Dissociation of sulfur hexafluoride tracer gas in the presence of an indoor combustion source

As an odorless, nontoxic, and inert compound, sulfur hexafluoride (SF6) is one of the most widely used tracer gases in indoor air quality studies in both controlled and uncontrolled environments. This compound may be subject to reactions with water vapor under elevated temperature to form acidic inorganic compounds such as HF and H2SO4. Thus, in the presence of unvented combustion sources such as kerosene heaters, natural gas heaters, gas log fireplaces, candles, and lamps, the SF6 dissociation may interfere with measurements of the emissions from these sources. Tests were conducted in a research house with a vent-free natural gas heater to investigate these potential interferences. It was observed that the heater operation caused about a 5% reduction of SF6 concentration, which can be an error source for the ventilation rate measurement and consequently the estimated pollutant emission rates. Further analysis indicates that this error can be much greater than the observed 5% under certain test conditions because it is a function of the ventilation flow rate. Reducing the tracer gas concentration has no effect on this error. A simple theoretical model is proposed to estimate the magnitude of this error. The second type of interference comes from the primary and secondary products of the SF6 dissociation, mainly H2SO4, SO2, HF, and fine particulate matter (PM). In the presence of approximately 5 ppm SF6, the total airborne concentrations of these species increased by a factor of 4-10. The tests were performed at relatively high SF6 concentrations, which is necessary to determine the interferences quantitatively. The second type of interference can be significantly reduced if the SF6 concentration is kept at a low ppb level.     

Persulfate oxidation for in situ remediation of TCE. I. Activated by ferrous ion with and without a persulfate-thiosulfate redox couple

The objective of the laboratory study is to examine the conditions under which transition metal ions (e.g., ferrous ion, Fe2+) could activate the persulfate anion (S2O8(2)-) to produce a powerful oxidant known as the sulfate free radical (SO4-*) with a standard redox potential of 2.6 V. The SO4-* is capable of destroying groundwater contaminants in situ such as trichloroethylene (TCE). Experiments using Fe2+ as an activator under various molar ratios of S2O8(2)-/Fe2+/TCE in an aqueous system indicated that partial TCE degradation occurred almost instantaneously and then the reaction stalled. Either destruction of SO4-* in the presence of excess Fe2+ or the rapid conversion of all Fe2+ to Fe3+ limited the ultimate oxidizing capability of the system. Sequential addition of Fe2+ in small increments resulted in an increased TCE removal efficiency. Therefore, it appeared that Fe2+ played an important role in generating SO4-*. An observation of oxidation-reduction potential (ORP) variations revealed that the addition of sodium thiosulfate (Na2S2O3) to the ferrous ion activated persulfate system could significantly decrease the strong oxidizing conditions. It was hypothesized that the thiosulfate induced reducing conditions might convert Fe3+ to a lower valence state of Fe2+, making the Fe2+ available to activate persulfate decomposition. The sequential addition of thiosulfate (S2O3(2)-), after the initial stalling of ferrous ion activated persulfate oxidation of TCE, resulted in an improvement in TCE removal. The ferrous ion activated persulfate-thiosulfate redox couple resulted in fairly complete TCE degradation in aqueous systems in a short time frame. In soil slurry systems, TCE degradation was slower in comparison to aqueous systems.     

电化学法去除SO2/NOX的研究进展

本文对采用电化学方法去除SO2/NOx废气这一新的研究方法进行了综述.在用酞花青钴(CoPc)修饰的碳气体扩散电极上,SO2在空气中的体积百分数在20%以下时可以完全被氧化为硫酸,以连二硫酸盐(S2O2-4)作还原剂,Fe2+-EDTA作络合剂时,NO以90%以上的程度还原为NH+4与NH2(SO3H)等低价含氮化合物,产物中未见N2、N2O与NO2等气体,氧化产物SO2-3(或HSO-3)在Pb阴极上还原再生为S2O2-4.用Ce4+作氧化剂可将SO2/NO2氧化为相应的酸,还原产物Ce3+经电解氧化后循环使用.     

Foliage responses of spruce trees to long-term low-grade sulfur dioxide deposition

Foliage on spruce trees (Picea rubens Sarg.) growing on dry SO(2) deposition zones (dry SO(2) deposition ranging from 0.5 and 8.5 S kg ha(-1) year(-1)) downwind from a SO(2) emission source was analyzed to assess chronic effects of long-term low-grade SO(2) deposition on net photosynthesis, stomatal conductance, dark respiration, stomatal antechamber wax structures, elemental concentrations in and on foliage (bulk and surficial concentrations), and types of epiphytic fungi that reside in the phylloplane. Elemental distributions on stomatal antechambers, on fungal colonies, and on smooth surfaces between stomates and fungus colonies were determined with a scanning electronic microscope (SEM) by way of X-ray scanning. It was found that net photosynthesis of newly developed spruce foliage (current-year, and 1-year-old) was not significantly affected by the local SO(2) deposition rates. Sulfur dioxide deposition, however, may have contributed to the gradual decrease in net photosynthesis with increasing needle age. Dark respiration rates were significantly higher on foliage taken from high SO(2) deposition zones. Stomatal rod-web structures deteriorated to flakes with increasing needle age and increasing SO(2) deposition. Further inspection of the needle surfaces revealed an increasing abundance of fungal colonies with increasing needle age. Many fungal taxa were isolated and identified. It was found that black yeasts responded positively, and Xylohypha pinicola responded negatively to high rates of SO(2) deposition. Surficial concentrations of elements such as P, S, K, Cl, Ca were about 10 times higher on fungal colonies than on smooth needle surfaces. Surficial Ca contents on 4 or 5-year-old needles decreased with increasing SO(2) deposition, but surficial S concentrations remained the same. In contrast, bulk foliar Ca and S concentrations increased with increasing SO(2) deposition.     

Removing and recovering gas-phase elemental mercury by Cu(x)Co(3-x)O(4) (0.75< or = x < or =2.25) in the presence of sulphur compounds

The Hg(0) oxidation ability and reusability of Cu(x)Co(3-x)O(4) were investigated in an attempt to improve SO(2) anti-poisoning ability of metal oxide and produce more economic and effective sorbents for the control of Hg(0) emission from combustion processes. The influence of copper content on Cu(x)Co(3-x)O(4)'s (0.75< or = x < or =2.25) oxidation ability of Hg(0) in the presence of SO(2) was investigated. According to the X-ray diffraction, Brunauer-Emmett-Teller (BET) and mass balance analysis on mercury, we found that Cu(1.5)Co(1.5)O(4) showed the highest S(BET) and best Hg(0) oxidation ability. With continuous increase of x from 0.75 to 2.25, Cu(x)Co(3-x)O(4)'s SO(2) anti-poisoning ability increased. The analysis results of the X-ray photoelectron spectroscopy manifested that the adsorptive mercury species on spent Cu(1.5)Co(1.5)O(4) was HgO. The spent Cu(1.5)Co(1.5)O(4) could be regenerated by thermal decomposition at 673K and regenerated Cu(1.5)Co(1.5)O(4) showed higher Hg(0) oxidation ability due to Hg-doping. Regenerated enrichment Hg(0) was collected using activated carbon at an ambient temperature to eliminate the secondary pollution.     

The promoter effect and a rate expression of the catalytic incineration of (CH3)2S2 over an improved CuO-MoO3/gamma-Al2O3 catalyst

The CuO-MoO3/gamma-Al2O3 catalyst, confirmed previously as having good activity in the catalytic incineration of (CH3)2S2, was employed as the principal catalyst in this study. With the aim of improving catalyst activity and resistance to deactivation by sulfur compounds, a promoter was added either before adding the precursors of Cu and Mo or together with Cu and Mo onto the gamma-Al2O3. Promoters included transition metals and elements from groups IA-VIIA in the chemical periodic table. Experimental results reveal Cr2O3 as the most effective promoter, with an optimal composition of 5 wt.% Cu, 6 wt.% Mo and 4 wt.% Cr (designated as Cu(5)-Mo(6)-Cr(4)/gamma-Al2O3). Knowing that higher acidity can improve activity, we further investigated the effect of acid treatment on the performance of the Cu(5)-Mo(6)-Cr(4)/gamma-Al2O3 catalyst. Experimental results indicate the H2SO4-treated catalyst (Cu(5)-Mo(6)-Cr(4)/sulfated-gamma-Al2O3) has a better activity and durability. A study for finding an appropriate rate expression for the catalytic incineration of (CH3)2S2 by Cu(5)-Mo(6)-Cr(4)/sulfated-gamma-Al2O3 was carried out in a differential reactor. The results show that the Mars-Van Krevelen model is applicable to this destructive oxidation reaction. Results additionally reveal that competitive adsorption of CH4 reduces conversion of (CH3)2S2.     

Temporal variation in daily concentrations of ozone and acid-related substances at Saturna Island, British Columbia

A multiple linear regression model was used to investigate seasonal and long-term trends in concentrations of ozone (O3) and acid-related substances at the Saturna Island monitoring station in southwestern British Columbia from 1991 to 2000. Statistically significant primary (dominant) cycles with a period of 1 yr were found for O3, sulfur dioxide (SO2), nitric acid (HNO3), and aerosol concentrations of sulfate (SO4(2-)), calcium (Ca2+) and chloride (Cl-). Of these, peak median concentrations occurred during the spring for O3 and Ca2+, during the warmer, drier months (April-September) for SO4(2-) and HNO3, and during the cooler, wetter months (October-March) for SO2 and Cl-. Statistically significant secondary cycles of 6 months duration were seen for concentrations of O3, SO4(2-), HNO3, Ca2+, and Cl-. Daily maximum O3 concentrations exhibited a statistically significant increase over the period of record of 0.33 +/- 0.26 ppb/yr. Statistically significant declines were found for concentrations of SO2, SO4(2-), HNO3, Ca2+, and potassium, ranging from 20 to 36% from levels at the start of the sampling period. Declines in ambient concentrations of SO2, SO4(2-), and HNO3 reflect local declines in anthropogenic emissions of the primary precursors SO2 and NOx over the past decade. Trends in Ca2+ and potassium ion concentrations are in line with a broader North American declining trend in acid-neutralizing cations.     

Characterization of fugitive material within a primary lead smelter.

The primary production of Pb via the sinter plant-blast furnace method resulted in a large number of Pb and other phases, reflecting the complex reactions occurring within each of the processes. Optical microscopy and X-ray diffraction (XRD) techniques have been used to characterize fugitive emissions and dusts generated during sintering, smelting, Cu drossing, refining, and slag fuming at a primary Pb-Zn smelter. The results displayed a complex array of phases, with the mineralogy of the dusts and fume reflecting conditions of the particular metallurgical operation. The principal Pb species followed a transformation from PbS through PbSO4 and PbO to Pb(o) (metal) from raw materials to the refinery. The fugitive emissions generated by the blast furnace were of a finer size with more complex chemistry than fugitive material from other source areas. XRD identified a mixture of PbS, ZnO, and ZnS, associated with one or more of the Cl-bearing phases Pb(OH)Cl, PbCl2, Pb4O3Cl2, Na3Pb2(SO4)3Cl, Pb10(SO4)Cl2O8, Pb4SCl6, and Pb7S2Cl10. The presence of Cl-bearing phases in the fume has possible health implications.     

Simultaneous removal of NO and SO2 by high-temperature fluidized zero-valent iron processes

A new approach to simultaneously remove nitrogen monoxide (NO) and sulfur dioxide (SO2) by zero valent iron (ZVI) was investigated. Three different parameters, temperature, flux, and ZVI dosage, were tested in fluidized ZVI column studies containing 500 ppmv of NO and SO2, respectively. Under the ZVI dosage of 0.5 g at flux of 0.6 L/cm2 x min for temperature 573 K, there is neither NO nor SO2 reduction. For 623 K and 673 K, complete removal for NO and > 90% removal for SO2 were achieved. For temperatures of 723 K and 773 K, 100% removal was achieved for both NO and SO2. The amounts of NO or SO2 reduction (as milligrams of NO or SO2 per gram ZVI) increased as temperature increased, and linearities were observed with both correlation coefficients > 0.97. Compared with NO, SO2 had earlier breakthrough because of a slower diffusion rate and less reactivity but higher mass reduction because of a higher molecular weight for SO2 (64 g/mol for SO2 and 30 g/mol for NO). At same temperature, both NO and SO2 reductions (as milligrams of NO or SO2 per gram of ZVI) were constant regardless of either flux or ZVI dosage variation, but breakthrough time was affected by both flux and ZVI dosage. A parameter weight of ZVI/flux (W/F) was developed to represent these two parameters at the same time to assess the breakthrough time of NO and SO2. Higher breakthrough time was achieved for higher W/F value. Moreover, interestingly, longer breakthrough time and more NO and SO2 mass reduction were achieved for combined NO and SO2 than individual NO or SO2 treated by ZVI, and both oxidation and reduction reactions occurred instead of a reduction reaction only. Chemical reactions among ZVI/NO, ZVI/ SO2, and ZVI/NO/SO2 were also proposed and verified by X-ray diffraction analyses.     

Response of needle sulphur and nitrogen concentrations of Scots pine versus Norway spruce to SO2 and NO2

The results of two field studies and an open-top chamber fumigation experiment showed that the response of mature Scots pine to SO(2) and NO(2) differed from that of mature Norway spruce. Moreover, the response of pine seedlings to SO(2) and NO(2) differed from that of mature trees. The greater increase in the needle total S concentrations of pine suggested more abundant stomatal uptake of SO(2) compared to spruce. Both pine seedlings and mature trees also seemed to absorb more N from atmospheric deposition. Mature pine was able to assimilate SO(4)(2-) derived from SO(2) into organic S more effectively than mature spruce at the high S and N deposition sites, whereas both pine and spruce seedlings accumulated SO(4)-S under NO(2)+SO(2) exposure. Spruce, in turn, accumulated SO(4)-S even when well supplied with N. Net assimilation of SO(4)(2-) in conifer seedlings was enhanced markedly by elevated temperature. To protect the northern coniferous forests against the harmful effects of S and N deposition, it is recommended that the critical level for SO(2) as a growing season mean be set at 5-10 microg m(-3) and NO(2) at 10-15 microg m(-3), depending on the 'effective temperature sum' and/or whether SO(2) and NO(2) occur alone or in combination.     

K2Cr2O7溶液同时脱硫脱硝实验研究

采用K2Cr2O7溶液作为吸收液,在自制的鼓泡反应器内,对模拟烟气进行同时脱硫脱硝的实验研究,考察多种因素对SO2脱除率(即脱硫率)和NO脱除率(即脱硝率)的影响。实验结果表明:K2Cr2O7浓度、反应温度、NO浓度、SO2浓度、烟气流量对脱硫率、脱硝率影响显著;当烟气流量为0.4L/min,气相中O2体积分数为6%,SO2体积分数为0.09%,NO体积分数为0.100%,K2Cr2O7摩尔浓度为10mmol/L,反应温度为40℃时,脱硫率、脱硝率分别达到100%和64.3%。     

A comparative study of the effects of chloride, sulfate and nitrate ions on the rates of decomposition of H2O2 and organic compounds by Fe(II)/H2O2 and Fe(III)/H2O2

The effects of chloride, nitrate, perchlorate and sulfate ions on the rates of the decomposition of hydrogen peroxide and the oxidation of organic compounds by the Fenton's process have been investigated. Experiments were conducted in a batch reactor, in the dark at pH < or = 3.0 and at 25 degrees C. Data obtained from Fe(II)/H2O2 experiments with [Fe(II)]0/[H2O2]0 > or = 2 mol mol(-1), showed that the rates of reaction between Fe(II) and H2O2 followed the order SO4(2-) > ClO4(-) = NO3- = Cl-. For the Fe(III)/H2O2 process, identical rates were obtained in the presence of nitrate and perchlorate, whereas the presence of sulfate or chloride markedly decreased the rates of decomposition of H2O2 by Fe(III) and the rates of oxidation of atrazine ([atrazine]0 = 0.83 microM), 4-nitrophenol ([4-NP]0 = 1 mM) and acetic acid ([acetic acid]0 = 2 mM). These inhibitory effects have been attributed to a decrease of the rate of generation of hydroxyl radicals resulting from the formation of Fe(III) complexes and the formation of less reactive (SO4(*-)) or much less reactive (Cl2(*-)) inorganic radicals.     

Removal of SO2 from simulated flue gases using non-thermal plasma-based microgap discharge

The removal of sulfur dioxide (SO2) from simulated flue gases streams (N2/O2/H2O/SO2) was experimentally investigated using microgap discharge. In the experiment, the thinner dielectric layers of aluminum oxide (Al2O3) were used to form the microgap discharge. With this physical method, a high concentration of hydroxyl (OH*) radicals were produced using the ionization of O2 and H2O to further the conversion of SO2 into sulfuric acid (H2SO4) at 120 degrees C in the absence of any catalysts and absorbents, which were captured with the electrostatic precipitator (ESP). As a result, the increase of discharge power and concentrations of O2 and H2O increased the production of OH. radicals resulting in enhanced removal of SO2 from gas streams. With the test and analysis, a number of H2SO4 droplets were produced in experiment. Therefore, a new method for removal of SO2 in semidry method without ammonia (NH3) additive was found.     

Response of a grassland ecosystem to air pollutants. VI. The chemical climate: concentrations and potential flux densities of relevant criteria pollutants

Of the so-called criteria air pollutants, ozone (O3) and sulfur dioxide (SO2) are relevant to agriculture due to their known toxic (O3, SO2) and fertilizing (SO2) potentials. A proper entity to describe pollutant doses in dose-response relationships is the cumulative flux density absorbed by the respective receptor systems. For nutrient budgets the whole ecosystem acts as receptor; for toxicological considerations, stomatal uptake has to be considered primarily. In Central Europe, the atmospheric inputs of oxidized S (SO2, SO3(2-) and SO4(2-)) have declined from the past, and at present are generally below the nutrient requirements of agroecosystems. In contrast, the phytotoxic potential of O3 has increased during the last decade. Pollutant absorbed doses and weighted concentrations were used to describe the risk potential. It could be shown that these two differ significantly.