Distinguishing Iron-Reducing from Sulfate-Reducing Conditions

Ground water systems dominated by iron‐ or sulfate‐reducing conditions may be distinguished by observing concentrations of dissolved iron (Fe²⁺) and sulfide (sum of H₂S, HS^?, and S⁼ species and denoted here as “H₂S”). This approach is based on the observation that concentrations of Fe²⁺ and H₂S in ground water systems tend to be inversely related according to a hyperbolic function. That is, when Fe²⁺ concentrations are high, H₂S concentrations tend to be low and vice versa. This relation partly reflects the rapid reaction kinetics of Fe²⁺ with H₂S to produce relatively insoluble ferrous sulfides (FeS). This relation also reflects competition for organic substrates between the iron‐ and the sulfate‐reducing microorganisms that catalyze the production of Fe²⁺ and H₂S. These solubility and microbial constraints operate in tandem, resulting in the observed hyperbolic relation between Fe²⁺ and H₂S concentrations. Concentrations of redox indicators, including dissolved hydrogen (H₂) measured in a shallow aquifer in Hanahan, South Carolina, suggest that if the Fe²⁺/H₂S mass ratio (units of mg/L) exceeded 10, the screened interval being tapped was consistently iron reducing (H₂～0.2 to 0.8 nM). Conversely, if the Fe²⁺/H₂S ratio was less than 0.30, consistent sulfate‐reducing (H₂～1 to 5 nM) conditions were observed over time. Concomitantly high Fe²⁺ and H₂S concentrations were associated with H₂ concentrations that varied between 0.2 and 5.0 nM over time, suggesting mixing of water from adjacent iron‐ and sulfate‐reducing zones or concomitant iron and sulfate reduction under nonelectron donor–limited conditions. These observations suggest that Fe²⁺/H₂S mass ratios may provide useful information concerning the occurrence and distribution of iron and sulfate reduction in ground water systems.     

Volcanic gases and sublimates from Showashinzan

Volcanic gases from Showashinzan are qualitatively the same as those liberated from igneous rocks when they are heated in vacuum. Their main components are H₂O, CO₂, and H₂. Then follow HCl, HF, N₂, SO₂, H₂S, S, CH₄, CO, Ar, Si, B, Mg, Na, K, Ca, Al, Fe, P, Br, NH₃, As, Zn, Sr, Ba, Cu, Pb, Sn, Sb, Bi, Ge, Ag, Cr, Ni, Mo, Rn, Ra, etc. They come through fumaroles of high temperature (～750°C.). Metallic compounds deposit as sublimates around the outlet of fumaroles. They are fractionated there according to their thermodynamic properties. When the temperature of gases falls, heavy metal elements deposit before reaching the surface of the earth. Ra is among them. Owing to the contribution of Ra thus depositted, Rn content of vapor is larger in low temperature fumaroles than in high temperature ones. Chemical compounds of H, C, N, O, and S vary their composition according to the condition of temperature and pressure. Sulfur exists as SO₂ more than H₂S. As the temperature of gases falls, SO₂ and H₂ decrease and H₂S increases. Mutual relation among them is ruled by the chemical equilibrium: SO₂+3H₂=H₂S+2H₂O. The structure of Showashinzan is not simple. Some deviations from the general rule are explained in connection with ground water.     

Sulphur isotope equilibrium during sulphur hydrolysis at high temperatures

Studies of the sulphur hydrolysis reaction, 4S + 4H₂O /ag 3H₂S + HSO₄^? + H⁺, were conducted between 200 and 320°C in sealed silica glass tubes. The isotope exchange reaction: H₂¹⁸O + HS¹⁶O₄^? /ag H₂¹⁶O + HS¹⁸O₄^? is so rapid at the low pH (1.5–3) as to be unquenchable. However, the sulphur isotope exchange reaction: H₂³⁴S+ H³²SO₄^? /ag H₂³²S + H³⁴SO₄^? gave t12 values of 0.1, 0.3 and 1.7 days at 320, 260 and 200°C respectively and equilibrium H₂S - HSO₄^? sulphur isotope fractionation values of 20.9, 22.4, 24.8, 26.7 and 29.3‰ at 320, 290, 260, 230 and 200°C respectively. This latter data is represented by: 1000lnα_(HSO4^??H2S) = 5.07 (10⁶T^?2) + 6.33, and has valuable applications in geothermal and ore deposit studies.     

Monitoring and mapping of hydrogen sulphide emissions across an active geothermal field: Rotorua,New Zealand

Hydrogen sulphide (H₂S) is one of a number of gaseous species associated with geothermal activity in the Taupo Volcanic Zone (TVZ), New Zealand. The city of Rotorua is located within Rotorua Caldera in the TVZ and is one of the few urban areas in the world where a large population (>60,000 people) is frequently exposed to geothermal emissions. In order to evaluate the health hazard from long-term exposure to H₂S being emitted from the Rotorua geothermal field, a passive sampler has been developed to measure concentrations of H₂S at many locations across the city simultaneously. In contrast to other passive or pump-based samplers, the sampler is inexpensive, easily mass-manufactured, and involves the reaction of H₂S with silver halide contained in treated photographic paper. H₂S-exposed paper shows a distinct colour change from white to dark brown as H₂S concentrations increase and is sensitive to concentrations between ≪30 and around 1000 ppb. Rotorua city can be divided into three regions—an area of low H₂S concentration in the west, a ‘corridor’ of high concentrations running north–south through the city centre where H₂S is being emitted, and an area of medium concentration to the east which is influenced by the prevailing wind direction, creating a plume from the central corridor. The data give new insight into the subsurface routes of degassing in the Rotorua geothermal field, by showing the surface expression of the main upflow zone and the direction of the conjectured faulting below.     

Origin of natural sulphur-bearing immiscible inclusions and H2S in oolite gas reservoir, Eastern Sichuan

Based on results of microscopic observation and laser Raman analysis about fluid inclusions, multiple special forms of immiscible inclusions that contain sulphur, liquid hydrocarbon, bitumen, etc. were discovered in samples collected from the H₂S gas reservoir-containing carbonates in the Lower Triassic Feixianguan Formation in the Jinzhu-Luojia area, Kai County, Sichuan Province. Based on the lithology and burial history of the strata involved as well as measurement results of homogenization temperature of fluid inclusions, bitumen reflectivity, etc., it is concluded that the H₂S in the gas reservoir resulted from the thermal reaction between hydrocarbons in reservoir and CaSO₄ in the gypsum-bearing dolostone section at the high temperature (140°C–17°C) oil-cracked gas formation stage in Late Cretaceous. Thereafter, research on a great number of immiscible inclusions in the reservoir reveals that elemental sulphur resulted from oxidation of part of the earlier-formed H₂S and further reaction between sulphates, hydrocarbons and H₂S in geological fluids in H₂S-bearing gas reservoir at a temperature of 86°C–89°C and a pressure of 340×10⁵Pa and during the regional uplift stage as characterized by temperature decrease and pressure decrease in Tertiary. Meanwhile, gypsum, anhydrite and calcite formed at this stage would trap particles like elemental sulphur and result in a variety of special forms of immiscible inclusions, and these inclusions would contain information concerning the complexity of the fluids in the reservoir and the origin of H₂S and natural sulphur in the gas reservoir.     

Removal of Hydrogen Sulfide by Physico‐Biological Filter Using Mixed Rice Husk Silica and Dried Activated Sludge

This study investigated the effectiveness of a new packing material, namely mixed rice husk silica with dried activated sludge for removing H₂S. Dried sewage sludge was collected from Putrajaya sewage treatment plant in Malaysia. Rice husk silica was prepared at temperature of 800°C, after acid leaching and mixed with dried sewage sludge to be utilized in a polyvinyl chloride filter. The system was operated under variable conditions of two parameters, different inlet gas concentration and different inlet flow rate. H₂S was passed through the filter with one liter of the packing material. More than 99.96% removal efficiency (RE) with empty bed residence time (EBRT) of 90–45 s and 300 ppm inlet concentration was observed. However, the RE decreased to 96.87% with the EBRT of 30 s. The maximum elimination capacity (EC) of 52.32 g/m³/h was obtained with the RE of 96.87% and H₂S mass loading rate of 54 g/m³/h, while at the RE of 99.96%, maximum EC was 26.99 g/m³/h with the H₂S mass‐loading rate of 27 g/m³/h. A strong significant correlation between increasing of H₂S mass loading rate and pressure drop was also detected (p < 0.01). Maximum pressure drop was 3.0 mm H₂O after 53 days of operating time, the EBRT of 30 s, and 54 g/m³/h of H₂S loading rate. These observations suggest that the mixture of rice husk silica with dried activated sludge is a suitable physico‐biological filter for H₂S removal.     

Determination of hydrogen sulfide in saline solutions

The glass/Ag⁰, Ag₂S electrode applicable for in situ determination of H₂S was tested in solutions of inert electrolytes. No effects on sensitivity, selectivity and slope were found up to an ionic strength of ≈0.7 (artificial seawater). In salty brines such as Dead Sea water or NaCl_sat. solution a positive potential shift and a slope increase was observed. This corresponds, presumably, to salting-out of the gas. Within the observed precision range of the detection method (+-3%) the electrode allows the measurement of H₂Sconcentrations (lower limit of detection: 10^−5.5 M S_tot). Nevertheless, as a consequence of its half cell combination, the electrode could be a means for the direct detection of the salting coefficient of H₂S in hypersaline media (I≫0.1).     

Mapping of H2S fluxes from the ground using copper passive samplers: An application study at the Zolforata di Pomezia degassing area (Alban Hills,Central Italy)

A new method for measuring H₂S mass flux from the ground, based on the digital analysis of the interference colours produced by the sulphidation of copper passive samplers (CPS), is proposed and discussed in this article. CPS sulphidation has a wide range of linear responses to H₂S doses and can be used together the accumulation chamber method to estimate gas fluxes from natural degassing areas. These are often characterized by the presence of vent centred degassing areas (VCDAs), which are recognizable from the absence or rarefaction of vegetation due to high acid gas concentrations in the soil pores and in the air at ground level. A reference emission curve, accounting for the advective and diffusive components of the flux, can be modelled and used to estimate the total H₂S mass released from each VCDA. The application of this method can be supported by remote sensing analysis that helps identify VCDAs in the field in perivolcanic H₂S degassing areas.As an illustrative application, H₂S gas fluxes from the ground were measured in spring 2007 at the Zolforata di Pomezia degassing area (ZPDA, Alban Hills, Central Italy) using an accumulation chamber internally equipped with CPS. H₂S peak fluxes were measured over the vents after remote sensing assisted identification of the VCDAs. Further measurements were carried out in two ponds and one artificial channel bordering the study area. The total atmospheric flux released at the ZPDA, estimated to be about 1207.6 kg day^? 1, was calculated as the summation of the fluxes from all the H₂S sources, the background flux being negligible.     

Contributions of H2S to the atmospheric sulfur cycle

H₂S is a most important biogenic sulfur compound with regard to the atmospheric sulfur cycle. Our present knowledge of the spatial and temporal distribution of this trace gas is rather incomplete owing to unreliable analytical methods. Therefore, a new method for the analysis of H₂S in the g-range was applied. This paper deals with the results of ground- and aircraft measurements of H₂S in unpolluted air over swamps and tidal flats. Based on the measured vertical distributions a removal coefficient of 2.3×10^–5 sec^–1 and an average lifetime of 12 hours were calculated. Some conclusions of the contribution of H₂S to the atmospheric sulfur budget are added.     

Gas and hydrogen isotopic analyses of volcanic eruption clouds in Guatemala sampled by aircraft

Gas samples were collected by aircraft entering volcanic eruption clouds of three Guatemalan volcanoes. Gas chromatographic analyses show higher H₂ and S gas contents in ash eruption clouds and lower H₂ and S gases in vaporous gas plumes. H isotopic data demonstrate lighter isotopic distribution of water vapor in ash eruption clouds than in vaporous gas plumes. Most of the H₂O in the vaporous plumes is probably meteoric. The data are the first direct gas analyses of explosive eruptive clouds, and demonstrate that, in spite of atmospheric admixture, useful compositional information on eruptive gases can be obtained using aircraft.     

Différenciation de l’émanation magmatique: réactions H2S + SO2 dans les gaz volcaniques. Vulcano (Italie), 1923–1979

Different systems of gas collection were tested on Vulcano Island (Italy). Sampling flasks do not keep the real H₂S/SO₂ ratio. Warm chemical traps (Sicardi, 1940) and warm field gas chromatography keep the gas samples in equilibrium. A mixture of H₂S and SO₂ is emitted at the crater but at the sea shore H₂S is predominant. Such difference is interpreted as due to the percolation across near-surface water tables. The same gas composition was observed within magmatic gases (Merapi) using identical techniques and the difference of composition at the shore and at the crater can be used to explain different aerosols compositions.     

Isotopic evidence of TSR origin for natural gas bearing high H<Subscript>2</Subscript>S contents within the Feixianguan Formation of the northeastern Sichuan Basin,southwestern China

The northeastern area of Sichuan Basin, southwestern China, is the area with the maximal reserve of natural gas containing higher hydrogen sulphide (H₂S) that has been found among the petroliferous basins of China, with the proven and controlled gas reserve of more than 200 billion cubic meters. These gas pools, with higher H₂S contents averaging 9%, some 17%, are mainly distributed on structural belts of Dukouhe, Tieshanpo, Luojiazhai, Puguang, etc., while the oolitic-shoal dolomite of the Triassic Feixianguan Fm. (T₁f) is the reservoir. Although many scholars regard the plentiful accumulation of H₂S within the deep carbonate reservoir as the result of Thermochemical Sulfate Reduction (TSR), however, the process of TSR as well as its residual geological and geochemical evidence is still not quite clear. Based on the carbon isotopic analysis of carbonate strata and secondary calcite, etc., together with the analysis of sulfur isotopes within H₂S, sulphur, gypsum, iron pyrites, etc., as well as other aspects including the natural gas composition, carbon isotopes of hydrocarbons reservoir petrology, etc., it has been proved that the above natural gas is a product of TSR. The H₂S, sulphur and calcite result from the participation of TSR reactions by hydrocarbon gas. During the process for hydrocarbons being consumed due to TSR, the carbons within the hydrocarbon gas participate in the reactions and finally are transferred into the secondary calcite, and become the carbon source of secondary calcite, consequently causing the carbon isotopes of the secondary calcite to be lower (−18.2‰). As for both the intermediate product of TSR, i.e. sulfur, and its final products, i.e. H₂S and iron pyrites, their sulfur elements are all sourced from the sulfate within the Feixianguan Fm. During the fractional processes of sulfur isotopes, the bond energy leads to the ³²S being released firstly, and the earlier it is released, the lower δ ³⁴S values for the generated sulphide (H₂S) or sulfur will be. However, for the anhydrite that participates in reactions, the higher the reaction degree, the more ³²S is released, while the less ³²S remains and the more δ ³⁴S is increased. The testing results have proved the process of the dynamic fractionation of sulfur isotopes.     

Fumarole/plume and diffuse CO2 emission from Sierra Negra caldera, Galapagos archipelago

Measurements of visible and diffuse gas emission were conducted in 2006 at the summit of Sierra Negra volcano, Galapagos, with the aim to better characterize degassing after the 2005 eruption. A total SO₂ emission of 11?±?2?t day^?1 was derived from miniature differential optical absorption spectrometer (mini-DOAS) ground-based measurements of the plume emanating from the Mini Azufral fumarolic area, the most important site of visible degassing at Sierra Negra volcano. Using a portable multigas system, the H₂S/SO₂, CO₂/SO₂, and H₂O/SO₂ molar ratios in the Mina Azufral plume emissions were found to be 0.41, 52.2, and 867.9, respectively. The corresponding H₂O, CO₂, and H₂S emission rates were 562, 394, and 3?t day^?1, respectively. The total output of diffuse CO₂ emissions from the summit of Sierra Negra volcano was 990?±?85?t day^?1, with 605?t day^?1 being released by a deep source. The diffuse-to-plume CO₂ emission ratio was about 1.5. Mina Azufral fumaroles released gasses containing 73.6?mol% of H₂O; the main noncondensable components amounted to 97.4?mol% CO₂, 1.5?mol% SO₂, 0.6?mol% H₂S, and 0.35?mol%?N₂. The higher H₂S/SO₂ ratio values found in 2006 as compared to those reported before the 2005 eruption reveal a significant hydrothermal contribution to the fumarolic emissions. ³He/⁴He ratios measured at Mina Azufral fumarolic discharges showed values of 17.88?±?0.25?R _A , indicating a mid-ocean ridge basalts (MORB) and a Galapagos plume contribution of 53 and 47?%, respectively.     

Aqueous volatiles in hydrothermal fluids from the Main Endeavour Field, northern Juan de Fuca Ridge: temporal variability following earthquake activity

The Main Endeavour Field, northern Juan de Fuca Ridge, experienced intense seismic activity in June 1999. Hydrothermal vent fluids were collected from sulfide structures in September 1999 and July 2000 and analyzed for the abundance of H₂, H₂S, CH₄, CO₂, NH₃, Mg and Cl to document temporal and spatial changes following the earthquakes. Dissolved concentrations of CO₂, H₂, and H₂S increased dramatically in the September 1999 samples relative to pre-earthquake abundances, and subsequently decreased during the following year. In contrast, dissolved NH₃ and CH₄ concentrations in 1999 and 2000 were similar to or less than pre-earthquake values. Aqueous Cl abundances showed large decreases immediately following the earthquakes followed by increases to near pre-earthquake values. The abundances of volatile species at the Main Endeavour Field were characterized by strong inverse correlations with chlorinity. Phase separation can account for 20-50% enrichments of CO₂, CH₄, and NH₃ in low-chlorinity fluids, while temperature- and pressure-dependent fluid-mineral equilibria at near-critical conditions are responsible for order of magnitude greater enrichments in dissolved H₂S and H₂. The systematic variation of dissolved gas concentrations with chlorinity likely reflects mixing of a low-chlorinity volatile-enriched vapor generated by supercritical phase separation with a cooler gas-poor hydrothermal fluid of seawater chlorinity. Decreased abundances of sediment-derived NH₃ and CH₄ in 1999 indicate an earthquake-induced change in subsurface hydrology. Elevated CO₂ abundances in vent fluids collected in September 1999 provide evidence that supports a magmatic origin for the earthquakes. Temperature-salinity relationships are consistent with intrusion of a shallow dike and suggest that the earthquakes were associated with movement of magma beneath the ridge crest. These data demonstrate the large and rapid response of chemical fluxes at mid-ocean ridges to magmatic activity and associated changes in subsurface temperature and pressure.     

Introductory notes on shock remanent magnetization and shock demagnetization of igneous rocks

Summary Effects of mechanical shocks of about 0.5 msec in duration on the remanent magnetization of igneous rocks are experimentally studied. The remanent magnetization acquired by applying a shock (S) in the presence of a magnetic field (H), which is symbolically expressed asJ _R (H₊S H_o), is very large compared with the ordinary isothermal remanent magnetization (IRM) acquired in the same magnetic field.J _R (H₊S H_o) is proportional to the piezo-remanent magnetization,J _R (H₊P₊P_o H_o).The effect of applyingS in advance of an acquisition of IRM is represented symbolically byJ _R (S H₊ H_o).J _R (S H₊ H_o) can become much larger than the ordinary IRM, and is proportional to the advance effect of pressure on IRM,J _R(P₊ P₀ H₊ H₀).The effect of shockS applied on IRM in non-magnetic space is represented by the shock-demagnetization effect,J _R(H₊ H₀ S), which also is proportional toJ _R(H₊ H₀ P₊ P₀).Because, the duration of a shock is very short, a single shock effect cannot achieve the final steady state. The effect ofn-time repeated shocks, is represented byJ ₀+J ^*(n), whereJ ₀ means the immediate effect and J ^*(n) represent the resultant effect of repeating, which is of mathematical expression proportional to [1–exp {–(n–1)}].

---

Zusammenfassung Die Effekte des mechanischen Stosses mit der Dauer von etwa 0.5 ms auf der remanenten Magnetisierung wurden experimentell nachgesucht. Das erworbene Remanenz der Magnetisierung nach dem Stoss (S) unter dem magnetischen Feld (H), das hier symbolisch alsJ _R(H₊ SH₀) bezechnet wird, ist sehr stark im Vergleich mit der normalen isothermischen remanenten Magnetisierung (IRM) unter demselben magnetischen Feld.J _R(H₊ S H₀) ist im Verhältnis zur piezoremanenten Magnetisierung,J _R(H₊ P₊ P₀ H₀).Der Effekt vom Stoss vor der Erwerbung von IRM wird symbolisch alsJ _R(S H₊ H₀) bezeichnet.J _R(S H₊ H₀) kann viel stärker als die normale IRM werden, im verhältnis zum Effekt des vorausgegebenen Drucks auf IRMJ _R(P₊ P₀ H₊ H₀).Der Effekt des Stosses auf IRM im Raum ohne magnetisches Feld wird mit dem Stossentmagnetisierungseffekt dargestellt,J _R(H₊ H₀ S), der auch proportional zuJ _R(H₊ H₀ P₊ P₀) ist.Da die Dauer einzelnen Stosses sehr kurz ist, kann der Effekt des einmaligen Stosses den endgültigen stabilen Zustand nicht erreichen. Der Effekt nachn-maligen wiederholten Stossen wird alsJ ₀+J ^*(n) bezeichnet, wobeiJ ₀ den unverzüglichen Effekt bedeutet, und J ^*(n) beschreibt den resultanten Effekt der Stosswiederholung, dessen mathematische Darstellung proporational zu [1–exp {–(n–1)}] ist.

     

H2S Emissions from a Submerged Pilot‐Scale Fixed Bed Biofilm Reactor

A study was performed in two submerged, pilot‐scale biofilm bioreactors operated under different conditions to determine the relationship between the operating parameters and H₂S emission. H₂S was always detected in the exhaust air at concentrations varying from 1 to 353 ppm_v. The specific aeration rate was the most influencing parameter, with As < 30 kg COD (dissolved oxygen concentrations <4 mg L^?1) increasing noticeably the H₂S production. The periodical removal of the accumulated sludge reduced H₂S emissions by ～14%.     

Multiple sulfur and oxygen isotope compositions in Beijing aerosol

Multiple sulfur isotopes(32S, 33 S, 34 S, 36S) and oxygen isotopes(16O, 18O) in Beijing aerosols were measured with MAT-253 isotope mass spectrometer. The δ34S values of Beijing aerosol samples range from 1.68‰ to 12.57‰ with an average value of 5.86‰, indicating that the major sulfur source is from direct emission during coal combustion. The δ18O values vary from 5.29‰ to 9.02‰ with an average value of 5.17‰, revealing that the sulfate in Beijing aerosols is mainly composed of the secondary sulfate. The main heterogeneous oxidation of SO2 in atmosphere is related to H2O2 in July and August, whereas H2O2 oxidation and Fe3+ catalytic oxidation with SO2 exist simultaneously in September and October. Remarkable sulfur isotope mass-independent fractionation effect is found in Beijing aerosols, which is commonly attributed to the photochemical oxidation of SO2 in the stratosphere. In addition, thermochemical reactions of sulfur-bearing compounds might be also a source of sulfur isotope anomalies based on the correlation between ?33S and CAPE.     

An isotope study of the accumulation mechanisms of high-sulfur gas from the Sichuan Basin,southwestern China

The mechanism of hydrogen sulfide (H₂S) generation plays a key role in the exploration and development of marine high-sulfur natural gas, of which the major targets are the composition and isotope characteristics of sulfur-containing compounds. Hydrocarbon source rocks, reservoir rocks, natural gases and water-soluble gases from Sichuan Basin have been analyzed with an online method for the content of H₂S and isotopic composition of different sulfur-containing compounds. The results of comparative analysis show that the sulfur-containing compounds in the source rocks are mainly formed by bacterial sulfate reduction (BSR), and the sulfur compounds in natural gas, water and reservoir are mainly formed by thermal sulfate reduction (TSR). Moreover, it has been shown that the isotopically reversion for methane and ethane in high sulfur content gas is caused by TSR. The sulfur isotopic composition of H₂S in natural gas is inherited from the gypsum or brine of the same or adjacent layer, indicating that the generation and accumulation of H₂S have the characteristics of either a self-generated source or a near-source.     

Toxic Effects of Copper‐Based and Synthetic Organic Pesticides on Activated Sludge

Toxic effects of five commonly used pesticides on the biomass of a municipal activated sludge system were determined on the basis of the reduction in the oxygen uptake rate (OUR) and specific oxygen uptake rate (SOUR). Toxicity levels of the selected pesticides were determined by employing a modified OECD 209 (Organisation for Economic Cooperation and Development) method which was performed as batch experiments using a respirometer. Copper sulphate (CuSO₄ · 5 H₂O), copper oxychloride (Cu₂Cl(OH)₃), copper calcium oxychloride (CaCu₃Cl₂(OH)₆) as copper‐based pesticides and chlorsulphuron (C₁₂H₁₂ClN₅O₄S), 2,4‐dichlorophenoxyacetic acid (2,4‐D) (C₈H₆Cl₂O₃) as synthetic organic pesticides were selected for the experiments. The EC₅₀ values were determined to be 78, 249 and 281 mg/L for CuSO₄ · 5 H₂O, Cu₂Cl(OH)₃ and CaCu₃Cl₂(OH)₆, respectively. Corresponding values for C₁₂H₁₂ClN₅O₄S and 2,4‐D were 860 and 3664 mg/L, respectively. Results indicated that toxicity effects of copper‐based pesticides were higher than that of synthetic organic pesticides. CuSO₄ · 5 H₂O was found to exert the highest toxicity among the copper‐based pesticides, whereas, C₁₂H₁₂ClN₅O₄S was determined to be the most toxic among the organic pesticides on activated sludge biomass.     

Forecast of volcanic eruptions by chemical methods

From the magmatic emanations differentiation point of view it is possible to calculate some ratios such as F/CO₂, Cl/CO₂, SO₂/CO₂, SO₂/H₂S, H₂S/CO₂ and CO₂/N₂ in the tumarolic gases for the forecasting of volcanic activity. In order to predict the cruptions of a volcano it is needed to select several fumaroles or hot springs having different regimes of variation of the above ratios. The study of some fumaroles composition at the Asama. Mihara, Kirishima and other volcanoes in Japan showed a close connection between volcanic gas compositions and state of the volcanoes.