Comparative studies of the Fe–UV, H2O2–UV, TiO2–UV/vis systems for the decolorization of a textile dye X-3B in water

The degradation of a common textile dye, Reactive-brilliant red X-3B, by several advanced oxidation technologies was studied in an air-saturated aqueous solution. The dye was resistant to the UV illumination (wavelength λ  320 nm), but was decolorized when one of Fe³⁺, H₂O₂ and TiO₂ components was present. The decolorization rate was observed to be quite different for each system, and the relative order evaluated under comparable conditions followed the order of Fe²⁺–H₂O₂–UV  Fe²⁺–H₂O₂ > Fe³⁺–H₂O₂–UV > Fe³⁺–H₂O₂ > Fe³⁺–TiO₂–UV > TiO₂–UV > Fe³⁺–UV > TiO₂–visible light (λ  450 nm) > H₂O₂–UV > Fe²⁺–UV. The mechanism for each process is discussed, and linked together for understanding the observed differences in reactivity.     

pH dependence of persulfate activation by EDTA/Fe(III) for degradation of trichloroethylene

The ability of free ferrous ion activated persulfate (S₂O₈²⁻) to generate sulfate radicals (SO₄⁻) for the oxidation of trichloroethylene (TCE) is limited by the scavenging of SO₄⁻ with excess Fe²⁺ and a quick conversion of Fe²⁺ to Fe³⁺. This study investigated the applicability of ethylene-diamine-tetra-acetic acid (EDTA) chelated Fe³⁺ in activating persulfate for the destruction of TCE in aqueous phase under pH 3, 7 and 10. Fe³⁺ and EDTA alone did not appreciably degrade persulfate. The presence of TCE in the EDTA/Fe³⁺ activated persulfate system can induce faster persulfate and EDTA degradation due to iron recycling to activate persulfate under a higher pH condition. Increasing the pH leads to increases in pseudo-first-order-rate constants for TCE, S₂O₈²⁻ and EDTA degradations, and Cl generation. Accordingly, the experiments at pH 10 with different EDTA/Fe³⁺ molar ratios indicated that a 1/1 ratio resulted in a remarkably higher degradation rate at the early stage of reaction as compared to results by other ratios. Higher persulfate dosage under the EDTA/Fe³⁺ molar ratio of 1/1 resulted in greater TCE degradation rates. However, increases in persulfate concentration may also lead to an increase in the rate of persulfate consumption.     

Azo-dyes photocatalytic degradation in aqueous suspension of TiO2 under solar irradiation

The photodegradation of two common and very stable azo-dyes, i.e. methyl-orange (C₁₄H₁₄N₃SO₃Na) and orange II (C₁₆H₁₁N₂SO₄Na), is reported. The photocatalytic oxidation was carried out in aqueous suspensions of polycrystalline TiO₂ irradiated by sunlight. Compound parabolic collectors, installed at the “Plataforma Solar de Almería” (PSA, Spain) were used as the photoreactors and two identical reacting systems allowed to perform photoreactivity runs for the two dyes at the same time and under the same irradiation conditions. The disappearance of colour and substrates together with the abatement of total organic carbon content was monitored. The main sulfonate-containing intermediates were found to be in lower number in respect to those obtained under artificial irradiation. In particular there were no more evidence of the presence of hydroxylated transients. The dependence of dye photooxidation rate on: (i) substrate concentration; (ii) catalyst amount; and (iii) initial pH was investigated. The influence of the presence of strong oxidant species (H₂O₂, S₂O₈²⁻) and some ions (Cl⁻, SO₄²⁻) on the process was also studied.     

TiO2纳米管催化活性再生处理技术简

采用H₂O₂、Fe₂（SO₄）₃和Fenton溶液对失活的TiO₂纳米管进行再生处理,重点考察了3种溶液的浓度和处理时间等对再生效果的影响,初步分析了经处理后TiO₂纳米管催化活性得到再生或增强的机理。结果表明,经H₂O₂溶液处理后TiO₂催化活性能得到有效再生,经Fe₂（SO₄）₃和Fenton溶液处理后其催化活性不仅得到再生,还能显著增强,这与H₂O₂和Fenton的强氧化作用,及进入TiO₂纳米管的Fe³⁺的阻止电子-空穴对再复合作用有关。     

天然沸石负载La2O3-ZnO-TiO2光催化降解活性艳红K-2BP

利用80目天然斜发沸石作载体制备La₂O₃(0.5%)-ZnO(20%)-TiO₂/沸石复合光催化剂,以20 W紫外灯为光源,在自制的光催化反应器中降解活性艳红K-2BP,考察了光照时间、空气通入量、催化剂用量、溶液初始浓度、H₂O₂与Fe³⁺投加量等对活性艳红K-2BP光催化降解率的影响。结果表明,当溶液初始浓度为60 mg/L,催化剂投加量为12 g/L,通气量为1 200 mL/min,光照2.5 h,活性艳红K-2BP的降解率可达99.2%;H₂O₂和Fe³⁺投加量为4 mL/L和3 g/L时,光照1 h活性艳红K-2BP降解率分别为100%和97.2%。紫外可见吸收光谱显示,LZTZ光催化剂可有效降解印染废水。     

Temporal and spatial relationships in fine particle strong acidity, sulphate, PM1O, and PM2.5 across multiple canadian locations

The Canadian Acid Aerosol Measurement Program (CAAMP) was established in 1992 to gain a better understanding of the atmospheric behaviour of fine particle strong acidity (“acid aerosols”) and to facilitate an assessment of the potential health risks associated with acid aerosols and particles in general. During 1992. 1993 and 1994, annular denuder and filter measurements were taken at four sites in Ontario, two in Quebec, three in the Atlantic Provinces and one in the greater Vancouver area. Mean fine particle sulphate concentrations (SO₄²⁻) were highest in southern Ontario (annual average ranged from 40–70 nmol m⁻³), lowest at a site in the Vancouver area (average = 16 nmol m⁻³) and second lowest in rural Nova Scotia. However, mean fine particle strong acid concentrations (H⁺) were geographically different. The highest mean concentrations were at the east coast sites (annual average of up to 30 nmol m⁻³). Acidities were lower in areas where the fine particle acidity experienced greater neutralization from reaction with ammonia. This included the major urban centres (i.e. Toronto and Montréal) and areas with greater amounts of agricultural activity, as in rural southern Ontario. On average, ambient concentrations of fine and coarse particle mass were larger in the urban areas and also in areas where SO₄²⁻ levels were higher. All the particle components were episodic. However, compared to SO₄²⁻ and fine particles (PM_2.5 or PM_2.1, depending upon inlet design), episodes of H⁺ tended to be less frequent and of shorter duration, particularly in Ontario. Saint John, New Brunswick, had the highest mean annual H⁺ concentration, which was 30 nmol m⁻³. H⁺ episodes (24 h concentration > 100 nmol m⁻³) were also the most frequent at this location. The high levels in Saint John were partially due to local sulphur dioxide sources and heterogeneous chemistry occurring in fog, which, on average, led to a 50% enhancement in sulphate, relative to upwind conditions.There was a substantial amount of intersite correlation in the day to day variations in H⁺, SO₄²⁻ , PM_2.5 and PM₁₀ (fine + coarse particles) concentrations, which is due to the influence of synoptic-scale meteorology and the relatively long atmospheric lifetime of fine particles. Sulphate was the most regionally homogenous species. Pearson correlation coefficients comparing SO₄²⁻ between sites ranged from 0.6 to 0.9, depending on site separation and lag time. In many cases, particle episodes were observed to move across the entire eastern portion of Canada with about a two-day lag between the SO₄²⁻ levels in southern Ontario and in southern Nova Scotia.     

X-ray absorption and photoelectron spectroscopy investigation of selenite reduction by Fe-bearing minerals

The long-lived radionuclide ⁷⁹Se is one of the elements of concern for the safe storage of high-level nuclear waste, since clay minerals in engineered barriers and natural aquifer sediments strongly adsorb cationic species, but to lesser extent anions like selenate (Se^VIO₄²⁻) and selenite (Se^IVO₃²⁻). Previous investigations have demonstrated, however, that Se^IV and Se^VI are reduced by surface-associated Fe^II, thereby forming insoluble Se⁰ and Fe selenides. Here we show that the mixed Fe^II/^III (hydr)oxides green rust and magnetite, and the Fe^II sulfide mackinawite reduce selenite rapidly (< 1 day) to FeSe, while the slightly slower reduction by the Fe^II carbonate siderite produces elemental Se. In the case of mackinawite, both S^−II and Fe^II surface atoms are oxidized at a ratio of one to four by producing a defective mackinawite surface. Comparison of these spectroscopic results with thermodynamic equilibrium modeling provides evidence that the nature of reduction end product in these Fe^II systems is controlled by the concentration of HSe⁻; Se⁰ forms only at lower HSe⁻ concentrations related to slower HSeO₃⁻ reduction kinetics. Even under thermodynamically unstable conditions, the initially formed Se solid phases may remain stable for longer periods since their low solubility prevents the dissolution required for a phase transformation into more stable solids. The reduction by Fe²⁺-montmorillonite is generally much slower and restricted to a pH range, where selenite is adsorbed (pH < 7), stressing the importance of a heterogeneous, surface-enhanced electron transfer reaction. Although the solids precipitated by the redox reaction are nanocrystalline, their solubility remains below 6.3 × 10^− 8 M. No evidence for aqueous metal selenide colloids nor for Se sorption to colloidal phases was found. Since Fe^II phases like the ones investigated here should be ubiquitous in the near field of nuclear waste disposals as well as in the surrounding aquifers, mobility of the fission product ⁷⁹Se may be much lower than previously assumed.     

Application of Fenton, photo-Fenton, solar photo-Fenton, and UV/H2O2 to degradation of the antineoplastic agent mitoxantrone and toxicological evaluation

In the present study, selected advanced oxidation processes (AOPs)—namely, photo-Fenton (with Fe²⁺, Fe³⁺, and potassium ferrioxalate—FeOx—as iron sources), solar photo-Fenton, Fenton, and UV/H₂O₂—were investigated for degradation of the antineoplastic drug mitoxantrone (MTX), frequently used to treat metastatic breast cancer, skin cancer, and acute leukemia. The results showed that photo-Fenton processes employing Fe(III) and FeOx and the UV/H₂O₂ process were most efficient for mineralizing MTX, with 77, 82, and 90 % of total organic carbon removal, respectively. MTX probably forms a complex with Fe(III), as demonstrated by voltammetric and spectrophotometric measurements. Spectrophotometric titrations suggested that the complex has a 2:1 Fe³⁺:MTX stoichiometric ratio and a complexation constant (K) of 1.47 × 10⁴ M^–1, indicating high MTX affinity for Fe³⁺. Complexation partially inhibits the involvement of iron ions and hence the degradation of MTX during photo-Fenton. The UV/H₂O₂ process is usually slower than the photo-Fenton process, but, in this study, the UV/H₂O₂ process proved to be more efficient due to complexing of MTX with Fe(III). The drug exhibited no cytotoxicity against NIH/3T3 mouse embryonic fibroblast cells when oxidized by UV/H₂O₂ or by UV/H₂O₂/FeOx at the concentrations tested.     

4种高级氧化法处理高浓度正丙醇废水的动力学比较

研究了1%和10%(V/V)模拟正丙醇废水在UV/TiO2体系、UV/H2O2体系、Fe2+/H2O2体系和UV/TiO2/Fe2+/H2O2体系等4种工艺条件下的降解动力学过程,对比了降解动力学特点及工艺参数对动力学常数的影响,优化工艺参数。结果表明,UV/TiO2体系和Fe2+/H2O2体系的降解过程可分为零级反应阶段和一级反应阶段,转折点分别在反应开始后2 h和氧化剂浓度为6.7 g/L,UV/H2O2体系和UV/TiO2/Fe2+/H2O2体系分别符合零级反应和一级反应规律;相同工艺参数条件下,6 h反应后,组合工艺UV/TiO2/Fe2+/H2O2体系在处理效率达85%,比前3个体系分别高52.0%、8.3%和32.0%,与UV/TiO2体系和Fe2+/H2O2体系的处理效率之和持平,其协同效应提高了速率常数,在目标物浓度降低时依然可维持较高降解速率。而目标物浓度提高10倍后,UV能量利用率提高35.5倍,氧化剂用量是Fe2+/H2O2体系的1/7.1。     

An aerosol flow tube study of the interaction of N2O5 with calcite, Arizona dust and quartz

The interaction of N₂O₅ with dispersed samples of Arizona Test Dust (ATD), Calcite (CaCO₃) and quartz (SiO₂) was investigated at varying relative humidity using an aerosol flow reactor. Reactive uptake coefficients, γ, obtained at close to zero relative humidity were (4.8 ± 0.7) × 10⁻³ for CaCO₃, (8.6 ± 0.6) × 10⁻³ for Quartz and (9.8 ± 1.0) × 10⁻³ for ATD. In the case of calcite, evidence was obtained for an enhanced rate of uptake at relative humidities above ≈ 50%. The results are compared to literature values obtained using bulk substrates and to previous aerosol uptake data on Saharan dust.     

Simultaneous E. coli inactivation and NOM degradation in river water via photo-Fenton process at natural pH in solar CPC reactor. A new way for enhancing solar disinfection of natural water

Bacteria inactivation and natural organic matter oxidation in river water was simultaneously conducted via photo-Fenton reaction at “natural” pH (6.5) containing 0.6 mg L⁻¹ of Fe³⁺ and 10 mg L⁻¹ of H₂O₂. The experiments were carried out by using a solar compound parabolic collector on river water previously filtered by a slow sand filtration system and voluntarily spiked with Escherichia coli. Fifty five percent of 5.3 mg L⁻¹ of dissolved organic carbon was mineralized whereas total disinfection was observed without re-growth after 24 h in the dark.     

O3/H2O2处理嘧啶废水的研究

采用O3/H2O2法对嘧啶废水进行处理,考察了不同反应条件对嘧啶和COD去除率的影响,并对O3/H2O2降解嘧啶的反应机制和动力学进行了初步探讨.实验结果表明,在pH值为11,反应时间为70 min,O3流量为4g/h,H2O2投加量为50 mmol/L的条件下,废水的嘧啶和COD的去除率分别达到86.46%和74.9...     

Synergistic increase in cell lethality by dieldrin and H2O2 in rat thymocytes: Effect of dieldrin on the cells exposed to oxidative stress

Dieldrin, one of persistent pesticides, is highly resistant to biotic and abiotic degradation. It is accumulated in organisms. Recent studies suggest that dieldrin exerts a potent cytotoxic action on cells exposed to oxidative stress. In this study, the effect of dieldrin on rat thymocytes exposed to hydrogen peroxide (H₂O₂)-induced oxidative stress was examined. Dieldrin at 5 μM and H₂O₂ at 300 μM slightly increased cell lethality from a control value of 5.4 ± 0.5% (mean ± standard deviation of four experiments) to 7.8 ± 1.3% and 9.0 ± 0.3%, respectively. Simultaneous application of dieldrin and H₂O₂ significantly increased cell lethality to 46.2 ± 1.8%. The synergistic increase in cell lethality was dependent on dieldrin concentration (0.3–5 μM) but not on H₂O₂ concentration (30–300 μM). Dieldrin accelerated H₂O₂-induced cell death, which was estimated with the help of annexin V-FITC and propidium iodide. Presence of either dieldrin or H₂O₂ decreased the cellular content of nonprotein thiol and increased intracellular Zn²⁺ concentration. The combination of dieldrin and H₂O₂ further pronounced these effects. TPEN, a chelator of intracellular Zn²⁺, significantly attenuated the synergistic increase in cell lethality induced by dieldrin and H₂O₂. It is, therefore, suggested that dieldrin augments the cytotoxicity of H₂O₂ in a Zn²⁺-dependent manner.     

Influence of operational key parameters on the photocatalytic decolorization of Rhodamine B dye using Fe2+/H2O2/Nb2O5/UV system

The present research deals with the development of a new heterogeneous photocatalysis and Fenton hybrid system for the removal of color from textile dyeing wastewater as Rhodamine B (RhB) solutions by using Fe²⁺/H₂O₂/Nb₂O₅ as a photocatalytic system. The application of this photocatalytic system for the decolorization of dye contaminants is not reported in the literature yet. Different parameters like dye concentration, Nb₂O₅/Fe²⁺ catalyst amount, pH, and H₂O₂ concentration have been studied. The optimum conditions for the decolorization of the dye were initial concentration of 10 mg L^?1 of dye, pH 4, and Nb₂O₅/Fe²⁺ catalyst concentration of 0.5 g L^?1/50 mg L^?1. The optimum value of H₂O₂ concentration for the conditions used in this study was 700 mg L^?1. Moreover, the efficiency of the Nb₂O₅/photo-Fenton hybrid process in comparison to photo-Fenton alone and a dark Fenton process as a control experiment to decolorize the RhB solution has been investigated. The combination of photo-Fenton and Nb₂O₅ catalysts has been proved to be the most effective for the treatment of such type of wastewaters. The results revealed that the RhB dye was decolorized in a higher percent (78 %) by the Nb₂O₅/photo-Fenton hybrid process (Fe²⁺/H₂O₂/Nb₂O₅/UV) than by the photo-Fenton process alone (37 %) and dark Fenton process (14 %) after 120 min of treatment. Moreover, the Nb₂O₅ catalyst as a heterogeneous part of the photocatalytic system was demonstrated to have good stability and reusability.     

Chemical characteristics of precipitation at metropolitan Newark in the US East Coast

To investigate the chemical characteristics of precipitation in the polluted coastal atmosphere, a total of 46 event-based precipitation samples were collected using a wet-only automatic precipitation collector from September 2006 to October 2007 at metropolitan Newark, New Jersey in the US East Coast. Samples were analyzed by ion chromatography for the concentrations of major inorganic ions (Cl⁻, NO₃⁻, SO₄²⁻, F⁻, NH₄⁺, Ca²⁺, Mg²⁺, Na⁺, K⁺) and organic acid species (CH₃COO⁻, HCOO⁻, CH₂(COO)₂²⁻, C₂O₄²⁻). Selected trace metals (Sb, Pb, Al, V, Fe, Cr, Co, Ni, Cu, Zn, Cd) in samples were determined by ICPMS. Mass concentration results show that SO₄²⁻ was the most dominant anion accounting for 51% of the total anions, controlling the acidity of the precipitation. NH₄⁺ accounted for 48.6% of the total cations, dominating the precipitation neutralization. CH₃COO⁻ and HCOO⁻ were the two dominant water-soluble organic acid species, accounting for 42% and 40% of the total organic acids analyzed, respectively. Al, Zn and Fe were the three major trace metals in precipitation, accounting for 34%, 27%, and 25% of the total mass of metals analyzed. The pH values in precipitation ranged from 4.4 to 4.9, indicating an acidic nature. Enrichment Factor (EF) Analysis showed that Na⁺, Cl⁻, Mg²⁺ and K⁺ in the precipitation were primarily of marine origin, while most of the Fe, Co and Al were from crust sources. Pb, V, Cr, Ni were moderately enriched with EFs ranging 43–410, while Zn, Sb, Cu, Cd and F⁻ were highly enriched with EFs > 700, indicating significant anthropogenic influences. Factor analysis suggests 6 major sources contributing to the observed composition of precipitation at this location: (1) nitrogen-enriched soil, (2) secondary pollution processes, (3) marine sources, (4) incinerations, (5) oil combustions, and (6) malonate–vanadium enriched sources. To further explore the source–precipitation event relationships and seasonality, cluster analysis was performed for all precipitation events. Results show that about half of the precipitation events were characterized by mixed sources. Significant influences of nitrogen-enriched soil and marine sources were associated with precipitation events in spring and autumn, while secondary pollution processes, incineration and oil combustion contributed greatly in summer.     

Fenton氧化法深度处理抗生素废水二级出水

采用Fenton氧化法对青霉素和土霉素混合废水二级处理出水进行深度处理,通过正交和单因素实验研究了废水初始反应pH值、H2O2投加量、Fe2+/H2O2摩尔比及反应时间等因素对废水处理效果的影响。实验结果表明,Fenton氧化法处理的最佳反应条件为:初始pH值4、H2O2(30%)投加量50 mL/L、Fe2+/H2O2摩尔比1/20和反应时间60 min,处理后出水COD小于120 mg/L,COD去除率在75%以上,急性毒性(HgCl2毒性当量)小于0.07 mg/L,满足《发酵类制药工业水污染物排放标准》(GB21903-2008)表2标准要求。     

Heterogeneous Fenton degradation of bisphenol A catalyzed by efficient adsorptive Fe3O4/GO nanocomposites

A new method for the degradation of bisphenol A (BPA) in aqueous solution was developed. The oxidative degradation characteristics of BPA in a heterogeneous Fenton reaction catalyzed by Fe₃O₄/graphite oxide (GO) were studied. Transmission electron microscopic images showed that the Fe₃O₄ nanoparticles were evenly distributed and were ～6 nm in diameter. Experimental results suggested that BPA conversion was affected by several factors, such as the loading amount of Fe₃O₄/GO, pH, and initial H₂O₂ concentration. In the system with 1.0 g L^?1 of Fe₃O₄/GO and 20 mmol L^?1 of H₂O₂, almost 90 % of BPA (20 mg L^?1) was degraded within 6 h at pH 6.0. Based on the degradation products identified by GC–MS, the degradation pathways of BPA were proposed. In addition, the reused catalyst Fe₃O₄/GO still retained its catalytic activity after three cycles, indicating that Fe₃O₄/GO had good stability and reusability. These results demonstrated that the heterogeneous Fenton reaction catalyzed by Fe₃O₄/GO is a promising advanced oxidation technology for the treatment of wastewater containing BPA.     

Fenton-like degradation of nalidixic acid with Fe3+/H2O2

The Fenton-like degradation of nalidixic acid was studied in this work. The effects of Fe³⁺ concentration and initial H₂O₂ concentration were investigated. Increasing the initial H₂O₂ concentration enhances the degradation and mineralization efficiency for nalidixic acid, while Fe³⁺ shows an optimal concentration of 0.25 mM. A complete removal of nalidixic acid and a TOC removal of 28 % were achieved in 60 min under a reaction condition of [Fe³⁺]?=?0.25 mM, [H₂O₂]?=?10 mM, T?=?35 °C, and pH?=?3. LC–MS analysis technique was used to analyze the possible degradation intermediates. The degradation pathways of nalidixic acid were proposed according to the identified intermediates and the electron density distribution of nalidixic acid. The Fenton-like degradation reaction of nalidixic acid mainly begins with the electrophilic attack of hydroxyl radical towards the C₃ position which results in the ring-opening reaction; meanwhile, hydroxyl radical attacking to the branched alkyl groups of nalidixic acid leads to the oxidation at the branched alkyl groups.     

Degradation of carbon tetrachloride by iron metal: Complexation effects on the oxide surface

Dehalogenation of chlorinated aliphatic contaminants at the surface of zero-valent iron metal (Fe⁰) is mediated by the thin film of iron (hydr)oxides found on Fe⁰ under environmental conditions. To evaluate the role this oxide film plays in the reduction of chlorinated methanes, carbon tetrachloride (CCl₄) degradation by Fe⁰ was studied under the influence of various anions, ligands, and initial CCl₄ concentrations ([P]_o). Over the range of conditions examined in these batch experiments, the reaction kinetics could be characterized by surface-area-normalized rate constants that were pseudo-first order for CCl₄ disappearance (k_CCl4), and zero order for the appearance of dissolved Fe²⁺ (k_Fe²⁺). The rate of dechlorination exhibits saturation kinetics with respect to [P]_o, suggesting that CCl₄ is transformed at a limited number of reactive surface sites. Because oxidation of Fe⁰ by CCl₄ is the major corrosion reaction in these systems, k_Fe²⁺ also approaches a limiting value at high CCl₄ concentrations. The adsorption of borate strongly inhibited reduction of CCl₄, but a concomitant addition of chloride partially offset this effect by destabilizing the film. Redox active ligands (catechol and ascorbate), and those that are not redox active (EDTA and acetate), all decreased k_CCl4 (and k_Fe²⁺). Thus, it appears that the relatively strong complexation of these ligands at the oxide–electrolyte interface blocks the sites where weak interactions with the metal oxide lead to dehalogenation of chlorinated aliphatic compounds.     

Recent trends in chemical composition of bulk precipitation at Estonian monitoring stations 1994–2001

Monthly and annual means of main anions (SO₄²⁻, NO₃⁻, Cl⁻) and summed base cations (Ca²⁺, Mg²⁺, K⁺, Na⁺) in bulk precipitation were studied at 10 stations during an 8-year monitoring period. The data showed statistically significant decreasing trends in most cases. Average declines of mean annual volume-weighted concentrations for both anions and cations were about two-fold. Despite the decrease, the loads of S and cations are still relatively high in Estonia (about 4–14 kg S ha⁻¹ and 0.6–1.2 keq ha⁻¹, respectively) compared with the loads in Finland and Sweden. Estimated linear decline trends followed the same pattern as annually combusted oil shale from Estonian power plants and emissions of SO₂ and fly ash. Recent trends in chemical composition of bulk precipitation at the monitoring stations reflected economic changes in Estonia as well as transboundary fluxes from neighbouring countries.