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.     

Brønsted reactions on oxide mineral surfaces and the temperature-dependence of their dissolution rates

The pH-dependence of oxide dissolution rates is controlled by Brønsted acid-base reactions at the mineral surface. These reactions are rapid but depend explicitly on temperature, as do the subsequent slow rates of bond hydrolysis. The net result is that dissolution rates vary in a complicated fashion with temperature and solution pH. The enthalpy changes of acid-base reactions on oxide materials are sufficiently similar, however, that general statements can be made about their contribution. The enthalpy changes from proton adsorption to a hydroxyl functional group (SOH), or to a deprotonated functional group (SO ^–), are generally exothermic. The enthalpy changes become increasingly endothermic, however, as charge accumulates on the mineral surface and the charged species interact electrostatically. The result is that mineral dissolution rates are least sensitive to temperature, as measured with an Arrhenius-like rate law, at pH conditions near the Point of Zero Net Proton Charge.     

Acid leaching of ash and coal: Time dependence and trace element occurrences

The leaching of coal and coal/asphaltite/wood-ashes in sulfuric acid (pH 1.0, 25 °C, S/L, 1:10) was studied as a function of time; acid consumption and extracted metal concentrations are presented. Whole coals consumed acid rapidly during the first few minutes, followed by slow acid consumption. Wood-, lignite-, and asphaltite-ashes consumed acid in two stages, the rapid phase extending < 30 min and the slow phase extended up to 10 days. The rapid phase was dominated by the dissolution of Ca, K and Mg ions for wood-ash, by Ca, Al and Mg ions for lignite-ash and Ca and Mg ions for asphaltite-ash. The sulfur concentration in solution and the concentrations of Ca, Fe, K, Mg, Na, P, Al and Mn in the aqueous phase verified the neutralizing capacity of the untreated ashes as well as the formation of insoluble sulfates in the residues. The slow phase kinetics differed for different fuels and exhibited leaching of several abundant elements—Fe, Al, K, Na and Mn. Trace elements (Ba, Cd, Co, Cr, Cu, Mo, Ni, Pb, Th, U, V, Zn) sometimes required up to 32 h for maximal extraction from ashes. Suggestions are presented regarding the chemical nature of trace elements in the untreated coals and ashes and suitable residence times for economical industrial processes. We think it possible to combine bacteriological oxidation of sulfidic concentrates of acid leaching from ash of various qualities or even whole coals.     

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.     

Attenuation of aqueous metal transport at two natural acid rock drainage occurrences in the Yukon Territory, Canada

Naturally acidic drainage associated with pyritic black shale has been observed in many locations in the Yukon Territory. While not necessarily linked to known mineral deposits, most of these natural acid rock drainage occurrences show elevated dissolved concentrations of trace elements, especially zinc, nickel, copper, cadmium and arsenic. Based on field observations, microbial investigation, chemical analyses and geochemical modeling, the fate and transport of potentially deleterious elements at two natural acid drainage occurrences with slightly different settings are examined. The Macintosh Creek is a small, acidic stream （pH 2.98-3.40）, 2 km long, located in the Macmillan Pass area of east-central Yukon amidst known sedimentary exhalative massive sulfide mineralization but remains undisturbed by exploration activities. Its trace metal content is apparently derived from groundwater discharges, which gave as much as 5.0, 2.5, 0.7, 0.13 and 0.03 mg/L ofZn, Ni, Cu and As, respectively. Interaction and sorption reactions with algal mats, biofilms and iron oxyhydroxides appear to be the dominant mechanisms attenuating aqueous contaminant transport along the stream. Cryogenic precipitation further consolidates the ferricrete formation and reduces the mobility of the sorbed metals. The tributaries of the Engineering Creek along the Dempster Highway in northern Yukon drain through a series of dolomite, phyllite, argillite, limestone, black shale, sandstone and conglomerate with no known concentration of mineralization. In this area, the water chemistry fully reflects the local geology with acidic streams invariably associated with black shale occurrences. Groundwater seeps in the headwaters area of the km-180 Creek completely enclosed in black shale gave pH 3.0 and as much as 148, 39, 2.9 and 9.1 mg/L of Zn, Ni, Cu and As, respectively. Sorption with iron oxyhydroxide and organic matter appear to dominate the attenuation of contaminant transport along the stream. However, once entered into carbonate-dominated terrains, secondary carbonate minerals exercise additional geochemical control on the local water chemistry as a result of neutralization.     

Naturally acidic and metalliferous waters at unmined volcanogenic massive sulfide deposits in the Bonnifield mining district, Alaska Range, east-central Alaska

The Bonnifield district hosts 26 tmmined volcanogenic massive sulfide （VMS） occurrences. Environmental geochemical samples of water and stream sediment were collected at several occurrences, concentrating on the two best-exposed and largest deposits, Red Mountain （RM） and Sheep Creek （SC）. Limited samples were also collected at the poorly exposed WTF deposit. The deposits are Late Devonian to Early Mississippian, and are hosted by felsic metavolcanic and carbonaceous schist members of the Totatlanika Schist or Keevy Peak Fm. Spring and stream waters at RM and SC have pH values commonly 〈3.5 （as low as 2.4 at RM and 2.5 at SC）, high conductivity （up to 11000 μS/cm）, and very high （Is to 100s mg/L） dissolved contents of Al, Cd, Co, Cu, Fe, Ni, and Pb. Waters at RM are characterized by extremely high REE contents （summed REE median 3200 μg/L, n=33）. At both RM and SC, pyrite oxidation and dissolution produce low pH waters that interact with and dissolve bedrock minerals, resulting in acidic, metal-laden, naturally degraded streams that are mostly devoid of aquatic life. Ferricrete is common. In contrast, WTF barely produces a surficial environmental footprint, mostly due to topography and relief. RM and SC are well exposed in the areas of relatively high relief, and both exhibit extensive areas of quartz-sericite-pyrite-alteration. While WTF shares many of the same deposit-and alteration characteristics, it is concealed by tundra in a large, nearly flat area. Surface water at WTF is absent and outcrops are sparse. Even though WTF is roughly the same size as Red Mountain （both around 3 million tonnes） and has similar base- and precious-metal grades, the surficial geochemical manifestation of WTF is minimal. However, exposure through mining of the altered, mineralized rock at WTF potentially could initiate the same processes of pyrite oxidation, acid generation, and mineral dissolution that are observed naturally at RM and SC.