Modelling and Optimization of Uranium (VI) Ions Adsorption Onto Nano-ZnO/Chitosan Bio-composite Beads with Response Surface Methodology (RSM)

Nano-ZnO-chitosan bio-composite beads were prepared for the sorption of \({\text{UO}}_{2}^{{2+}}\) from aqueous media. The resulting nano-ZnO/CTS bio-composite beads were characterized by TEM, XRD etc. The sorption of \({\text{UO}}_{2}^{{2+}}\) by bio-composite beads was optimized using RSM. The correlation between four variables was modelled and studied. According to RSM data, correlation coefficients (R²?=?0.99) and probability F-values (F?=?2.24?×?10^??10) show that the model fits the experimental data well. Adsorption capacity for nano-ZnO/CTS bio-composite beads was obtained at 148.7 mg/g under optimum conditions. The results indicate that nano-ZnO/CTS bio-composite beads are appropriate for the adsorption of \({\text{UO}}_{2}^{{2+}}\) ions from aqueous media. Also, the suitability of adsorption values to adsorption isotherms was researched and thermodynamic data were calculated.     

Magnetic Cr(VI) Ion Imprinted Polymer for the Fast Selective Adsorption of Cr(VI) from Aqueous Solution

In this study, a novel magnetic Cr(VI) ion imprinted polymer (Cr(VI)-MIIP) was successfully synthesized and used as a selective sorbent for the adsorption of Cr(VI) ions from aqueous solution. It can be synthesized through the combination of an imprinting polymer and magnetic nanoparticles. The high selectivity achieved using MIIP is due to the specific recognition cavities for Cr(VI) ions created in Cr(VI)-MIIP. Also, the magnetic properties that could be obtained using magnetic nanoparticles, helps to separate adsorbent with an external magnetic field without either additional centrifugation or filtration procedures. The magnetic Fe₃O₄ nanoparticles (MNPs) were synthesized using an improved co-precipitation method and modified with tetraethylorthosilicate (TEOS) before imprinting. The magnetic Cr(VI) ion imprinted polymer was prepared through precipitation copolymerization of 4-vinylpyridine as the complexing monomer, 2-hydroxyethyl methacrylate as a co-monomer, the Cr⁶⁺ anion as a template, and ethylene glycol dimethacrylate (EGDMA) as a cross-linker in the presence of modified magnetite nanoparticles. This novel synthesized sorbent was characterized using different techniques. Batch adsorption experiments were performed to evaluate the adsorption conditions, selectivity, and reusability. The results showed that the maximum adsorption capacity was 39.3 mg g^?1, which was observed at pH 3 and at 25?°C. The equilibrium time was 20 min, and the amount of adsorbent which gave the maximum adsorption capacity was 1.7 g L^?1. Isotherm studies showed that the adsorption equilibrium data were fitted well with the Langmuir adsorption isotherm model and the theoretical maximum adsorption capacity was 44.86 mg g^?1. The selectivity studies indicated that the synthesized sorbent had a high single selectivity sorption for the Cr(VI) ions in the presence of competing ions. Thermodynamic studies revealed that the adsorption process was exothermic (\(\Delta H\)?<?0) and spontaneous (\(\Delta G\)?<?0). In addition, the spent MIIP can be regenerated up to five cycles without a significant decrease in adsorption capacity.     

Gasification and reforming of biomass and waste samples by means of a novel catalyst

This study conducted gasification and catalytic reforming experiments with the expectation of obtaining new advantages on energy recovery and aimed for the development of an effective catalyst. Initially, the use of thermal gasification technology for waste treatment in line with waste-to-energy strategies was reviewed. Technological systems which have gasification were classified and their current status was discussed. Then, the results of gasification and reforming experiments showed that product gas with 50 % H₂ or more was obtained using a Ni catalyst on a mesoporous silica–based SBA-15 support (NiO/SBA-15), which we newly developed. Experiments using wood feedstock revealed that H₂ production by the catalyst was better when the NiO content was 20 % (W/W) or more than when another catalyst or the Ni catalyst with a lower Ni loading was used. Tar formation as a by-product was also well controlled by the catalyst, and use of a catalyst with 40 % NiO reduced the tar concentration to less than 0.2 g/\( {\text{m}}^{3}_{\text{N}} \). Experiments using a mixed feedstock of wood and RPF resulted in an increase in hydrocarbon concentration because of insufficient reforming. This finding suggests that future work is required to find a better solution to wood and RPF co-gasification.     

Acid Rain in Downtown São Paulo City, Brazil

During the period from July 2002 to June 2004, the chemical characteristics of the rainwater samples collected in downtown São Paulo were investigated. The analysis of 224 wet-only precipitation samples included pH and electrical conductivity, as well as major ions (Na⁺, $ \rm NH^{ + }_{4} During the period from July 2002 to June 2004, the chemical characteristics of the rainwater samples collected in downtown S?o Paulo were investigated. The analysis of 224 wet-only precipitation samples included pH and electrical conductivity, as well as major ions (Na⁺, , K⁺, Ca²⁺, Mg²⁺, Cl⁻, , ) and carboxylic acids (acetic, formic and oxalic) using ion chromatography. The volume weighted mean, VWM, of the anions , and Cl⁻ was, respectively, 20.3, 12.1 and 10.7 μmol l⁻¹. Rainwater in S?o Paulo was acidic, with 55% of the samples exhibiting a pH below 5.6. The VWM of the free H⁺ was 6.27 μmol l⁻¹), corresponding to a pH of 5.20. Ammonia (NH₃), determined as (VWM = 32.8 μmol l⁻¹), was the main acidity neutralizing agent. Considering that the H⁺ ion is the only counter ion produced from the non-sea-salt fraction of the dissociated anions, the contribution of each anion to the free acidity potential has the following profile: (31.1%), (26.0%), CH₃COO⁻ (22.0%), Cl⁻ (13.7%), HCOO⁻ (5.4%) and (1.8%). The precipitation chemistry showed seasonal differences, with higher concentrations of ammonium and calcium during autumn and winter (dry period). The marine contribution was not significant, while the direct vehicular emission showed to be relevant in the ionic composition of precipitation.     

Aerobic thermophilic bacteria enhance biogas production

The enhancing effect of aerobic thermophilic (AT) bacteria on the production of biogas from anaerobically digested sewage sludge (methanogenic sludge) was investigated. Sewage sludge (5%, w/w) was incubated at 65°C with shaking for a few months to prepare the AT seed sludge. AT sludge was prepared by incubation of the AT seed sludge (5%, v/v) and sewage sludge (5%, w/w) at 65°C with shaking. The addition of this AT sludge (1.2% ± 0.5% of total volatile solids) to methanogenic sludge enhanced the production of biogas. The optimum volume of the addition and the pretreatment temperature of the AT sludge for optimum biogas production were 5% (v/v) and 65°C. Batch-fed anaerobic digestion was covered with the addition of various AT sludges. The AT sludge prepared with the AT seed sludge improved the biogas production by 2.2 times relative to that from the sewage sludge addition. The addition of sludge without AT seed sludge weakly enhanced biogas production. An aerobic thermophilic bacterium (strain AT1) was isolated from the AT seed sludge. Strain AT1 grew well in a synthetic medium. The production of biogas from the anaerobic digestion of sewage sludge was improved by the addition of 5% (v/v) AT1 bacterial culture compared with that from the sewage sludge addition. The addition of AT1 culture reduced the volatile solids by 21%, which was higher than the 12.6% achieved with the sewage sludge addition. The AT1 bacterial culture enhanced the biogas production more than the AT seed sludge. The phylogenetic analysis of the 16S rRNA gene revealed that strain AT1 is closely related to Geobacillus thermodenitrificans (100% sequence similarity). The improvement in the production of biogas with the AT sludge could be caused by thermophilic bacterial activity in the AT sludge.     

Tensile Properties of Polylactide/Poly(ethylene glycol) Blends

The blends of polylactide (PLA) and poly(ethylene glycol) (PEG) with different contents (0, 5, 10, 15, and 20 wt%) and molecular weights (\( \overline{M}_{w} \) 6000, 10,000 and 20,000, called respectively as PEG 6000, PEG 10,000, and PEG 20,000) were prepared by means of melt blending method. The effects of tensile speed, content and molecular weight of the PEG on the tensile properties of the PLA/PEG blends were investigated using a universal testing machine at 24 °C. With increasing tensile speed, the tensile modulus, strength and stress at break of the PLA/PEG blends marginally increased, while the tensile modulus and stress at break declined non-linearly, and the tensile strength dropped nearly linearly with increasing PEG 10,000 content. When the PEG 10,000 content was 5–15 wt%, the tensile strain at break of the PLA/PEG 10,000 blend markedly increased, and then decreased as the PEG 10,000 content exceeded 15 wt%. With increasing the molecular weight of PEG, tensile modulus and strength increased, whereas the tensile strain at break decreased. This showed that the application of right amount of lower molecular weight PEG was more conducive to improving the tensile toughness of the PLA/PEG blends, which was attributed to its better miscibility with PLA and increased mobility of PLA molecular chains.     

Analysis of the combustion and pyrolysis of dried sewage sludge by TGA and MS

In this study, the combustion and pyrolysis processes of three sewage sludge were investigated. The sewage sludge came from three wastewater treatment plants.Proximate and ultimate analyses were performed. The thermal behaviour of studied sewage sludge was investigated by thermogravimetric analysis with mass spectrometry (TGA-MS). The samples were heated from ambient temperature to 800 °C at a constant rate 10 °C/min in air (combustion process) and argon flows (pyrolysis process). The thermal profiles presented in form of TG/DTG curves were comparable for studied sludges. All TG/DTG curves were divided into three stages. The main decomposition of sewage sludge during the combustion process took place in the range 180–580 °C with c.a. 70% mass loss. The pyrolysis process occurred in lower temperature but with less mass loss. The evolved gaseous products (H₂, CH₄, CO₂, H₂O) from the decomposition of sewage sludge were identified on-line.     

Distributions,Land-source Input and Atmospheric Fluxes of Methane in Jiaozhou Bay

CH₄ concentrations in both the surface and bottom waters of Jiaozhou Bay were determined during four surveys in 2003, which showed variability with both seasons and tidal cycles. Atmospheric fluxes of CH₄ in Jiaozhou Bay showed obvious seasonal and spatial variations, with the highest values occurring in summer and the lowest in winter. The annual emission of CH₄ from Jiaozhou Bay was estimated to be . CH₄ in the water column of Jiaozhou Bay was found to come from several land-sources including riverine water input, sewage water input and groundwater input. The spatial and temporal variation in distributions and atmospheric fluxes of CH₄ in Jiaozhou Bay was influenced mainly by the input of polluted river waters and the sewage effluents along the eastern coast, which highlights the effects of human impacts on CH₄ emission rates.     

Gasification characteristics of sewage sludge combined with wood biomass

The gas products from gasification processes have been considered to have some limitations in gas composition and heating value from the previous studies. Gasification characteristics of sewage sludge and wood mixture were investigated using different mixing ratios with the purpose of better quality of gas product suitable for energy/power generation. The gasification experiment was performed by an indirectly heated fluidized bed reactor. As reaction temperature increased from 600 to 900 °C, the yield of gas product increased with higher generation of CO, H₂ and CH₄ by more activated gas conversion reactions. As the equivalence ratio increased from 0.2 to 0.4, composition ratio of CO₂ increased while CO, CH₄, H₂ decreased as expected. Several operating variables including mixing ratio of wood with dried sludge were also tested. From this initial stage of experiment, optimal operating conditions for the bubbling fluidized bed gasifier, could be considered 900 °C in temperature; 0.2 in equivalence ratio and 40 % in wood mixing ratio within test variables range. These results will be more thoroughly investigated for the application to the larger scale pilot system.     

Mercury emission from sewage sludge incineration in Japan

Sewage sludge contains trace amounts of mercury, and sewage sludge incineration is a major source of mercury emissions. However, relatively few studies have reported on mercury emissions from sewage sludge incineration. Consequently, data on emissions from sewage sludge incinerators must be updated to estimate current emissions of mercury. In this study, we examined mercury emissions and speciation using continuous mercury analyzers in two incinerators. The mercury concentrations in stack gas from facilities A and B were 36.6 and 21.1???g/Nm³, respectively. As a result, the emission rate was calculated to be 0.282?C0.750?g/ton-dry sludge. Considering the total amount of sewage sludge incinerated in Japan, the mercury emissions from sewage sludge incinerators were estimated to be 0.49?C1.31?tons/year.     

Reusability of sewage sludge in clay bricks

Bricks produced from sewage sludge in different compositions were investigated. Results of the tests indicated that the sludge proportion is a key factor in determining the brick quality. Increasing the sludge content results in a decrease in brick shrinkage, bulk density, and compressive strength. Brick weight loss on ignition was mainly due to the contribution of the contained organic matter from the sludge being burnt off during the firing process, as well as inorganic substances found in both clay and sludge. The physical, mechanical, and chemical properties of the bricks that were supplemented with various proportions of dried sludge from 10 to 40wt% and generally complied with the General Specification for Brick as per the Malaysian Standard MS 7.6:1972, which dictates the requirements for clay bricks used in walling in general. A standard leaching test method also showed that the leaching of metals from the bricks is very low.     

Modelling Phosphorus Retention in Lakes and Reservoirs

Steady-state models for the prediction of P retention coefficient (R) in lakes were evaluated using data from 93 natural lakes and 119 reservoirs situated in the temperate zone. Most of the already existing models predicted R relatively successfully in lakes while it was seriously under-estimated in reservoirs. A statistical analysis indicated the main causes of differences in R between lakes and reservoirs: (a) distinct relationships between P sedimentation coefficient, depth, and water residence time; (b) existence of significant inflow–outflow P concentration gradients in reservoirs. Two new models of different complexity were developed for estimating R in reservoirs: , where τ is water residence time (year), was derived from the Vollenweider/Larsen and Mercier model by adding a calibrated parameter accounting for spatial P non-homogeneity in the water body, and is applicable for reservoirs but not lakes, and , where [P_in] is volume-weighted P concentration in all inputs to the water body (μg l⁻¹), was obtained by re-calibrating the OECD general equation, and is generally applicable for both lakes and reservoirs. These optimised models yield unbiased estimates over a large range of reservoir types.     

Dynamic studies on lead volatilization from CaO–SiO2–Al2O3 molten slag under N2–CO–CO2, N2–HCl and N2–H2S gas atmospheres

Dynamic studies on the volatilization of lead from CaO–SiO₂–Al₂O₃ molten slags were conducted in a lab-scale melting furnace from 1623 to 1773 K under different mixed gas atmospheres of CO 0.05–0.3 atm to CO₂ 0–0.3 atm to N₂ (balance), HCl 1.7 × 10^?3–6.7 × 10^?3 atm to N₂ (balance), and H₂S 3.0 × 10^?4 to 1.7 × 10^?3 atm to N₂ (balance). The slag samples consisted of the mixed powders of 20–50 wt% CaO, 30–60 wt% SiO₂, and 10–40 wt% Al₂O₃, containing 2000 ppm PbO.Results showed that the rates of volatilization of lead from the CaO–SiO₂–Al₂O₃ molten slags under the N₂–CO–CO₂, N₂–HCl, and N₂–H₂S gas atmospheres were higher than those under the simulated air (N₂–O₂), which increased with CO, HCl, and H₂S partial pressures. At \(p_{{HCl}}\)  =  \(p_{H_{2}S}\)  = 1.7 × 10^?3 atm, the apparent rate constants for the volatilization of lead under the N₂–H₂S and N₂–HCl gas atmospheres were nearly equal, which increased with a rise in temperature. Results also showed that the rate of volatilization of lead from the molten slag decreased drastically with the increasing viscosity of the molten slag, in the viscosity range lower than 3 Pa s. Consequently, the volatilization of lead from the CaO–SiO₂–Al₂O₃ molten slag was significantly influenced by CO, HCl, and H₂S partial pressures and by the viscosity of the molten slag.     

Effect of thermochemical pretreatment on sewage sludge and its impact on carboxylic acids production

This paper investigates the potential of converting sewage sludge into a useful product, namely carboxylic acids. To potentially enhance acid yields, the effect of pretreatment using 0.3 g lime/g dry biomass and water at 100 °C for 10–240 min was studied. The pretreated sludges were anaerobically fermented to mixed-acids using a mixed culture of microorganisms; methanogens were suppressed using iodoform. Batch fermentations were performed at 55 °C using ammonium bicarbonate buffer. The first batch experiments compared treated and untreated sludge as the only substrate. The second batch experiments used a mixture of sludge plus lime-treated bagasse (20:80 by weight). Analysis of liquor shows that the pretreatment were effective in solubilizing constituent compounds of sewage sludge. Nitrogen content and carboxylic acids increased with increasing pretreatment time. However, the soluble sugars peaked at 60 min, and then decreased with longer pretreatment time, showing that the solubilised sugars were undergoing intermolecular reactions, such as Maillard reactions. Fermentation experiments were a good indicator of the biodegradability of the pretreated sludges. Results clearly showed that lime-treating sludge, using even the minimum pretreatment time (10 min), negatively impacted acid production. The likely causes of this observation are attributed to the production of recalcitrant complexes and toxic compounds. Batch fermentation of untreated sludge yielded 0.34 g total acids/g VS fed, whereas sludge with 240-min lime pretreatment yielded only 0.20 g total acids/g VS fed. Co-fermentation of untreated sludge with pretreated bagasse gave a yield of 0.23 g total acids/g VS fed.     

Development of a high-efficiency rotary dryer for sewage sludge

A rotary drum dryer having an internal rotating body was designed and tested in this study. It was shown that the developed dryer is effective for drying sewage sludge. The best operating conditions in the dryer were low energy input and almost 10% moisture content. The conditions are 255°C for the rotary drum temperature, 17 min for the sludge residence time, and 55 kg/m³ h for the dryer load. Under these conditions, the drying efficiency was 84.8%. The average diameter of dried sludge was less than 8 mm, and the weight reduction rate was 80%. Parametric screening studies achieved the following results. The drying efficiency increased with the increase of the internal temperature and the sludge residence time in the rotary drum, while the drying efficiency decreased when increasing the dryer load. In addition, it was shown that NH₃ and CO₂ were the primary components released from the sewage sludge drying process. The amounts of both of these components increased when the rotary drum temperature was increased.     

Laboratory appraisal of organic carbon changes in mixtures made with different inorganic wastes

Mixtures of organic and inorganic wastes were incubated to examine the changes in organic C (OC) contents. An anaerobic sludge and a CaO-treated aerobic sludge, with OC concentrations of 235 and 129 g kg^?1, were used. The inorganic wastes used – referred to as “conditioners” – were shot blasting scrap, fettling, Linz-Donawitz slag, foundry sand (FS), and fly ash from wood bark combustion (FA). The total OC (TOC) and ${\text{KMnO}}_4^{?}$ oxidized OC were determined. DTA-TGA profiles and FTIR spectra were also obtained. Mixtures made with the FS contained significantly lower (P < 0.05) amounts of TOC (45 g kg^?1) than the rest of mixtures, which was attributed to the non-existence of reactive surfaces in the conditioner and the increased aeration induced by this material. Those made with FA contained significantly higher (P < 0.05) amounts of TOC (170 g kg^?1), which was attributed to: (i) the addition of an extra source of C – black carbon (BC) – in the FA, and (ii) the inhibition of mineralization from the compounds present in this conditioner (e.g., amorphous aluminosilicates, BC). The results highlight the importance of the characteristics of the conditioners on the fate of the OM originating from the sludges.     

Preparation,sintering behavior,and expansion performance of ceramsite filter media from dewatered sewage sludge,coal fly ash,and river sediment

The main aim of this study is to assess the preparation, sintering behavior, and expansion performance of ceramsite filter media (CFM) from dewatered sewage sludge, coal fly ash, and river sediment without using any natural resources. The results showed that the investigated physical properties of lab made CFM met with the China’s industrial standard of CJ/T 299-2008 and the concentration of heavy metals in the lixivium was lower than the threshold of GB 5085.3-2007. During the sintering process, the relationships between ignition loss rate, expansion rate, and sintering temperature could be well described simultaneously by the 3-order polynomial fitting curve, with high correlation coefficient values (R ² > 0.999). The fitting curves of the ignition loss rate and expansion rate had one peak and one valley, respectively, and their cut-off point that is the sintering temperatures were the same (700 °C). The whole sintering process could be divided into two stages. The ignition loss rate was gradually increased in both the stages. At the same time, the expansion rate was decreased in the first stage and then increased in the second stage. The significance of this work is to pursue the concept of sustainable development.     

Fate of mutagenic chemicals in soil amended with petroleum and wood preserving sludges

A field study using monoliths (lysimeters) of a sandy clay loam soil was conducted to assess the fate of mutagenic chemicals after refinery and wood preserving bottom sediment sludges were land treated. The Ames Salmonella/microsome assay¹ was used to determine the direct (without metabolic activation, −S9) and indirect (with metabolic activation, + S9) mutagenicity of the wastes, unamended soil, waste amended soils, and leachate. Extracts having a mutagenic ratio (MR) (MR= No. colonies from sample extract/No. colonies from DMSO solvent control) of ⩾ 2 were considered positively mutagenic. Extracts of the wood preserving waste sludge without activation were non-mutagenic (MR < 2) but extracts with activation ( + S9) produced very strong indirect mutagenicity (MR = 7.9). After soil incorporation, the waste amended soil produced very strong direct (MR = 8.9) and indirect (MR = 11.9) mutagenicity by day 180 and remained mutagenic (MR = 5.7, −S9; MR = 3.95, + S9) through day 350. The amount of residue in leachate from the wood preserving waste amended lysimeters was significantly greater (P <0.05) than the unamended soil during the first 90 days after waste application, but was not different after 90 days. The leachate residue from wood preserving waste amended lysimeters in the 90–180-day period produced mutagenic responses both with (MR = 2.24 and 2.51) and without (MR = 2.29) activation. Polynuclear aromatic hydrocarbons were the main constituents identified in the leachate residues that produced a mutagenic response. Soil treatment of the refinery sludge reduced its weak indirect mutagenicity before soil incorporation (MR = 2) to non-mutagenic (MR = 1.4) immediately following soil treatment. The MR of the waste amended soil increased to 1.7 by day 180 but by day 350 decreased to a level equal to that observed at day 0 (MR = 1.4). Leachate from the refinery amended lysimeters had significantly greater (P < 0.05) amounts of organic residue than unamended lysimeters 180 to 350 days after waste application. The leachate from one refinery waste amended lysimeter (90–180 days after waste application) produced a mutagenic response (MR = 3.16). The refinery sludge was detoxified shortly after soil treatment, but the wood preserving sludge required > 350 days to detoxify in the soil environment. The possibility exists that mobile mutagenic chemicals may leach into underlying groundwater from the treatment zone of soils amended with refinery and wood preserving sludges.     

Leaching characteristics and phytotoxic effects of sewage sludge biochar

Biochar was prepared via the pyrolysis of sewage sludge at temperatures ranging from 300 to 900 °C and the physical–chemical compositions of the biochars obtained were analyzed. Leaching tests were conducted using the biochars to investigate the release of the constituents and their phytotoxic effects on wheat (Triticum aestivum) seeds in a germination test. Multivariate analyses were used to evaluate the contributions of the constituents to the germination index (GI). The results showed that the biochars were rich in micronutrient contents and they improved the germination of wheat. The heavy metal contents were higher in the biochars than the sewage sludge and their levels increased with the pyrolysis temperature, but they were within the acceptable limits for land application, thereby suggesting that sewage sludge is suitable for use as a biochar substrate. The different components of the biochar leachates could promote and inhibit the germination of wheat seeds, where the GI was promoted at lower concentrations but inhibited at higher concentrations. Our results suggest that biochar is an effective and environmentally friendly fixative for the immobilization of heavy metals in sewage sludge when applied to land or disposed of in landfill, but its ecotoxicity needs to be assessed to ensure its environmental safety.     

Trends in Chemical Composition of Wet-only Precipitation at Rural French Monitoring Stations Over the 1990–2003 Period

The long-term monitoring of precipitation and its chemical composition are important for identifying trends in rain quality and for assessing the effectiveness of pollution control strategies. A statistical test has been used to the atmospheric concentrations measured in the French rural monitoring network (MERA) in order to bring out spatio-temporal trends in precipitation quality in France over the period 1990–2003. The non-parametric Mann–Kendall test which has been developed for detecting and estimating monotonic trends in the time series was used and applied in our study at annual values of wet-only precipitation concentrations. The emission data suggest that SO₂ and NO _x emissions decreased (−3.3 and −2.0% year⁻¹, respectively) contrary to NH₃ emissions that increased slightly (+0.2% year⁻¹) over the period 1990–2002 in France. On the national scale, the pH values have a significant decreasing trend of −0.025 ± 0.02 unit pH year⁻¹. and concentrations in precipitation have a significant decreasing trend, −3.0 ± 1.6 and −3.3 ± 0.6% year⁻¹, respectively, corresponding with the downward trends in SO₂ emissions in France (−3.3% year⁻¹). A good correlation (R ² = 0.84) between SO₂ emissions and concentrations was obtained. The decreasing trend of was more significant (−5.4 ± 5.2% year⁻¹) than that of (−1.3 ± 2.4% year⁻¹). Globally, the concentration of the major ions showed a clear downward trend including marine and alkaline ions. In addition, the relative contribution of HNO₃ to acidity precipitation increased by 51% over the studied period.