Kinetics of redox cycling of iron coupled with fulvic acid

The kinetics of conversion of iron(III) (hydr)oxides to ferrous iron mediated by fulvic acid have been investigated in order to improve the understanding of the redox cycling of iron at the oxic-anoxic boundary in natural waters. Under the conditions similar to natural waters, fulvic acid is able to reduce the iron(III) (hydr)oxide. The kinetics of the reaction depend on the reactivity of iron(III) (hydr)oxides and the reducing power of the fulvic acid. The rate of reaction is 60 nm/h obtained under following conditions: total concentration of Fe(III) 1.0 × 10^–4 M, pH 7.5, fulvic acid 5 mg/L. The rate is considered as a net result of reduction and oxidation in the > Fe^III-OH/Fe(II) wheel coupled with fulvic acid. In a real natural water system, reductants other than fulvic acid may be of importance. The results obtained in the laboratory, however, provide evidence that the Fe(OH)₃(s)/Fe(II) redox couple is able to act as an electron-transfer mediator for the oxidation of natural organic substances, such as fulvic acid by molecular oxygen either in the absence of microorganisms or as a supplement to microbial activity.     

Latitudinal variation of measured O3 photolysis frequencies J(O1D) and primary OH production rates over the Atlantic Ocean between 50° N and 30° S

The latitudinal variation of the photolysis frequency of ozone to O(¹D) atoms, J(O¹D), was measured using a filter radiometer during the cruise ANT VII/1 of the research vessel Polarstern in September/October 1988. The J(O¹D) noon values exhibited a maximum of 3.6×10^-5 s^-1 (2 sr) at the equator and decreased strongly towards higher latitudes. J(O¹D) reached highest values for clean marine background air with low aerosol load and almost cloudless sky. The J(O¹D) data, measured under these conditions and a temperature of 295 K, can be expressed by: % MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaamOsaiaacI% cacaqGpbWaaWbaaSqabeaaiiaacqWF8baFaaGccaqGebGaaeykaiaa% bccacqWF9aqpcaqGGaGaaeyzaiaabIhacaqGWbGaaeiiaiaabUhacq% GHsislcaaI4aGaaiOlaiaaicdacaaIYaGaeyOeI0IaaGioaiaac6ca% caaI4aGaaiiEaiaaigdacaaIWaWaaWbaaSqabeaacqGHsislcaaIZa% aaaOGaaeiiaiaabIhacaqGGaGaam4uaiabgUcaRiaaiodacaGGUaGa% aGinaiaacIhacaaIXaGaaGimamaaCaaaleqabaGaeyOeI0IaaGOnaa% aakiaadofadaahaaWcbeqaaiaaikdaaaGccaGG9bGaaeikaiaaboha% daahaaWcbeqaaiabgkHiTiaaigdaaaGccaGGPaaaaa!5EE9!\[J({\text{O}}^| {\text{D) }} = {\text{ exp \{ }} - 8.02 - 8.8x10^{ - 3} {\text{ x }}S + 3.4x10^{ - 6} S^2 \} {\text{(s}}^{ - 1} )\] where S represents the product of the overhead ozone column (DU) and the secant of the solar zenith angle. The meridional profile of the primary OH radical production rate P(OH) was calculated from the J(O¹D) measurements and simultaneously recorded O₃ and H₂O mixing ratios. While the latitudinal distribution of J(O¹D) and water vapour was nearly symmetric to the equator, high tropospheric ozone levels up to 40 ppb were observed in the Southern Hemisphere, SH, resulting in higher P(OH) in the SH.     

Using numerical modelling to evaluate tsunami hazard near the Kuril Island

A sequence of computer experiments is used to study questions concerning the tsunami problem as a quantitative estimate of tsunami danger, detailed geographical tsunami classification, determination of the parameters of critical tsunami waves, and the conditions of their development. We call a wave critical, if its impact on the coast is most hazardous.Using the Middle Kuril Island as an example, we present the results of a computer experiment which includes determining the wavefields on the shelf and estimating the effects connected with the deep-water Bussol and Diana Straits.Numerical simulation of tsunami waves of different sources permits the assessment of the extent of tsunami danger in different areas of the coastal zone of Simushir Island, depending on the location of the focus zone and their geometry.The major singularities of the wavefield arise in the zones of the deep-water straits. The distribution of the amplification factors is determined by both the global parameters of the wavefields and the local properties of individual harbours. The results obtained for a particular harbour in the northern part of Simushir Island, formed the basis for the quantitative estimate of tsunami danger for this area.     

Trace gas exchange at the air/water interface: Measurements of mass accommodation coefficients

A liquid jet of 90 m diameter and variable length has been utilized to determine absorption rates and, hence, mass accommodation coefficients , of atmospheric trace gases. The compounds investigated are HCl (0.01), HNO₃ (0.01), N₂O₅ (0.005), peroxyacetyl nitrate (>0.001), and HONO (0.005). It is concluded that the absorption of these trace gases by liquid atmospheric water is not significantly retarded by interfacial mass transport. The strengths and limitations of the liquid jet technique for measuring mass accommodation coefficients are explored.     

Fracture analysis in the south-western Corinth rift (Greece) and implications on fault hydraulic behavior

This paper reviews the data concerning the fracture network and the hydraulic characteristics of faults in an active zone of the Gulf of Corinth. Pressure gap measured through fault planes shows that in this area the active normal faults (Aigion, Helike) act, at least temporarily and locally, as transversal seal. The analysis of the carbonate cements in the fractures on both the hangingwall and the footwall of the faults also suggests that they have acted as local seals during the whole fault zone evolution. However, the pressure and the characteristics of the water samples measured in the wells indicate that meteoric water circulates from the highest part of the relief to the coast, which means it goes through the fault zones. Field quantitative analysis and core studies from the AIG-10 well have been performed to define both regional and fault-related fracture networks. Then laboratory thin section observations have been done to recognize the different fault rocks characterizing the fault zone components. These two kinds of approach give information on the permeability characteristics of the fault zone. To synthesize the data, a schematic conceptual 3D fluid flow modeling has been performed taking into account fault zone permeability architecture, sedimentation, fluid flow, fault vertical offset and meteoric water influx, as well as compaction water flow. This modeling allows us to fit all the data with a model where the fault segments act as a seal whereas the relays between these segments allow for the regional flow from the Peloponnese topographic highs to the coast.     

Subsurface thermal and hydrothermal characterization based on geothermal resources map, drill hole thermal gradients, Curie point depths and hypocenter distribution — Examples of Tohoku district, Japan

Subsurface thermal structure in Tohoku district are characterized by existing data such as geothermal resources maps, drill hole thermal gradients, Curie point depths and hypocenters distribution maps. The collected data are registered in a database system, then, compared in plan view, cross-section and bird's-eye pictures. The comparison indicates that subsurface temperatures extrapolated from drill hole thermal gradients are generally concordant to the Curie point depth, assumed to be 650 °C. Tohoku district is generally divided into 5 type areas; fore arc lowland, fore arc mountain country, Quaternary volcanic terrain, back arc lowland and back arc mountain country. The surface thermal manifestations in Quaternary volcanic terrain are mainly controlled by the magma chambers as heat sources, while, surface thermal features such as hot springs in non-volcanic areas are controlled by degrees of heat flows, and hydrothermal flows in permeable Cenozoic formations and along permeable fault zones.     

Possibility of degradation of phenylarsonic acid in the presence of ferrihydrite

Although inorganic species are predominant in natural systems, but there are many kinds of organoarsenic species such as methylated and phenylated arsenic compounds. Phenylarsonic acid （PA） is a degradation product of organoarsenics used for chemical warfare agents, which has been detected in well water at the disposal site of the agents in Japan. There are few reports studying behavior of PA in soil. In this study, PA was adsorbed onto ferrihydrite and its chemical forms were determined using high performance liquid chromatography connected to inductivity-coupled plasma mass spectrometry （HPLC-ICP-MS）. 100 mg/kg of PA was mixed with 0.03 g of 2-line ferrihydrite. For each suspension, pH was adjusted by HNO3 or NaOH. Each sample was incubated for more than 19 hours and the final pH was measured. After filtration, the chemical form of arsenic in the filtrate was measured using HPLC-ICP-MS. In addition, ferrihydrite separated by filtration was dissolved by 3 ml of 0.5 M HCI and the arsenic species in the solution was detected by HPLC-ICP-MS （column： Tosoh TSKgel SuperlC-AP, eluent： 0.01 M HNO3）. It was verified that PA is not degraded by heating in 0.5 M HCl solution. At pH 3.1, any arsenic compounds were not detected from the solution, because almost all arsenic species were adsorbed onto ferrihydrite at lower pH. At pH= 12, however, 7%-10% of inorganic arsenic was detected in the solution. In solid phase, there are some problems to determine the precise ratio of inorganic and organic species. When the solution includes Fe ion at 0.01 M level, the retention time of arsenic species drifted compared to those in standard solution, which makes it difficult to determine precisely the arsenic species adsorbed on ferrihydrite. Therefore, more study is needed to determine the ratio of inorganic and organic species in the system.     

Effects of low molecular weight organic acids on sorption and desorption behavior of p-chlorophenol by yellow earth

Low molecular weight organic acids （LMWOAs） are important components of root exudates. They play an important role in immobilizing and remobilizing contaminants in rhizospheric soil. Effects of four LMWOAs on the sorption and desorption behavior of p-chlorophenol by yellow earth was studied in batch mode. The results showed that the previous application of LMWOAs to enhanced adsorption capacity of p-chlorophenol of the soil in the order of maleic acid〉malic acid〉oxalic acid〉citric acid. However, when LMWOAs were applied to soil where p-chlorophenol had been previously adsorbed, substantial p-chlorophenol was desorbed from soil by oxalic acid, whereas citric acid, malic acid and maleic acid didn＇t desorb as much p-chlorophenol from soil as deionized water.     

The acid neutralizing capacity （ANC） of South Africa＇s freshwater ecosystems

Acidification is considered the most important one of the primary chemical stress factors that impact on freshwater ecosystems. In unpolluted freshwater systems, the primary controls on the degree of acidification are factors such as the geological substrate of the catchment area, the presence of organic acids secreted by vegetation in the river system, and equilibrium exchange of carbon dioxide with the atmosphere. Anthropogenic factors that can impact on the degree of acidification of freshwater systems include agricultural, mining and industrial activities, either through direct runoff into river systems or through deposition of atmospheric pollutants from these sources. The capacity factors alkalinity and acidity, which represent the acid- and base-neutralizing capacity （ANC and BCN） of an aqueous system, have been used as more reliable measures of the acidic character of freshwater systems than pH. Unlike pH, ANC and BNC are not affected by parameters such as temperature and pressure. Therefore, ANC has been employed as a predictor of biological status in critical load assessments. Freshwater systems with ANC＇s eq/L isμeq/L are considered sensitive to acidification, ANC=0 μbelow 150 commonly used as the predictor for fish species such as trout in lakes, and an eq/L as more realistic for streams. Acid-neutralizing capacity μANC value of 40 （ANC） can be determined by titration with a strong acid to a preselected equivalence point. Alternatively, it can be calculated as the difference between base cations （[BC]） and strong acid anions （[SAA]）： ANC=[BC]- [SAA]=[Ca^2＋]＋[Mg^2＋]＋[Na^＋]＋[K^＋]-[SO4^2-]-[NO3^-]-[Cl^-] To date, there has been no attempt to establish the ANC of South Africa＇s freshwater ecosystems or variability therein, despite the fact that long-term water quality monitoring data exist for all the parameters needed to calculate it according to the above equations. As a result, the relationship between the acid neutralizing capacity of freshwater ecosystems in South Africa and biodiversity factors, such as fish status, is unknown. Results of the first comprehensive （country-wide scale） evaluation of the acid neutralizing capacity of river systems in South Africa will be presented. Long-term monitoring data obtained from the Department of Water Affairs and Forestry （DWAF） from most of South Africa＇s river systems were used to establish geographic and temporal variabilities in ANC. The results show that the Berg and Breede River systems are most susceptible to acidification, and that geological substrate appears to explain most of the geographic variabilities observed.     

The effect of acid deposition on base cation cycling in a karstic-forested catchment： Evidence from strontium isotopes

Bedrock weathering and atmospheric deposition are the two primary sources of base cations （K^＋, Na^＋, Ca^2＋ and Mg^2＋） to forest ecosystems. Therefore, the key problem is to understand the relative inputs from these two sources and the cycling in the ecosystem. This study focuses on the effects of acid deposition on cation cycling in a small-forested karstic catchment in Guizhou Province. Sr isotope ratios were used as a tracer for understanding the transport process between the different cation pools： rock, soil, surface water, atmospheric deposition and plant. The samples of wet deposition, total deposition, throughfall, surface and ground waters, vegetation, and soil were monthly collected. The exchangeable Sr^2＋ and Ca^2＋ in soil samples were extracted by using 1 M ammonium acetate. The leaf-tissue samples were ashed at 550℃, and the residue was digested in ultrapure HClO4 and HNO3. All water samples were filtrated through 0.45 μm aperture filter paper. Base cation concentrations and Sr isotopic composition were analyzed for all the samples. The results show that acid deposition （average pH 4.9） frequently occurred in the studied region. Cation abundance follows an increasing manner from rainwater, throughfall, to surface water or ground water samples, suggesting that acid deposition at first eiuviates Ca^2＋ , Mg^2＋ and Sr^2＋ from leaf, then the exchangeable cations from soil, and at last cations accumulate in surface water or ground water.