Rate constants for the reactions of the NO3 radical with HCOOH/HCOO− and CH3COOH/CH3COO− in aqueous solution between 278 and 328 K

The kinetics of the aqueous phase reactions of NO₃ radicals with HCOOH/HCOO^– and CH₃COOH/CH₃COO^– have been investigated using a laser photolysis/long-path laser absorption technique. NO₃ was produced via excimer laser photolysis of peroxodisulfate anions (S₂O ₈ ^2– ) at 351 nm followed by the reactions of sulfate radicals (SO ₄ ^– ) with excess nitrate. The time-resolved detection of NO₃ was achieved by long-path laser absorption at 632.8 nm. For the reactions of NO₃ with formic acid (1) and formate (2) rate coefficients ofk ₁=(3.3±1.0)×10⁵ l mol^–1 s^–1 andk ₂=(5.0±0.4)×10⁷ l mol^–1 s^–1 were found atT=298 K andI=0.19 mol/l. The following Arrhenius expressions were derived:k ₁(T)=(3.4±0.3)×10¹⁰ exp[–(3400±600)/T] l mol^–1 s^–1 andk ₂(T)=(8.2±0.8)×10¹⁰ exp[–(2200±700)/T] l mol^–1 s^–1. The rate coefficients for the reactions of NO₃ with acetic acid (3) and acetate (4) atT=298 K andI=0.19 mol/l were determined as:k ₃=(1.3±0.3)×10⁴ l mol^–1 s^–1 andk ₄=(2.3±0.4)×10⁶ l mol^–1 s^–1. The temperature dependences for these reactions are described by:k ₃(T)=(4.9±0.5)×10⁹ exp[–(3800±700)/T] l mol^–1 s^–1 andk ₄(T)=(1.0±0.2)×10¹² exp[–(3800±1200)/T] l mol^–1 s^–1. The differences in reactivity of the anions HCOO^– and CH₃COO^– compared to their corresponding acids HCOOH and CH₃COOH are explained by the higher reactivity of NO₃ in charge transfer processes compared to H atom abstraction. From a comparison of NO₃ reactions with various droplets constituents it is concluded that the reaction of NO₃ with HCOO^– may present a dominant loss reaction of NO₃ in atmospheric droplets.     

A preliminary study of the carbon-isotopic content of ambient formic acid and two selected sources: Automobile exhaust and formicine ants

Relatively large quantities (1 mg) of formic acid have been collected from the atmosphere and subjected to carbon-isotopic analysis, as a means of source discrimination. Ambient formic acid was captured on Ca(OH)₂-treated filters using a high-volume sampler. The collection method was not only efficient (>96%), but also appears to have low artifact production.Most of the samples (36 out of 52) were collected over a two-year period at the summit of Mount Lemmon, Arizona, where a strong seasonality in HCOOH mixing ratio was observed (0.2 ppb during winter months to 1.5 ppb in the summer). Other collection sites included the Oregon coast, Colorado Rockies, urban Tucson, and the North Dakota prairie. The carbon-13 content of atmospheric HCOOH was found to be have little variation (–18 to –25), regardless of location or season. This is consistent with a single dominant source of formic acid. The carbon-14 measurements of 6 Mount Lemmon samples showed high levels of modern carbon (93–113% modern).The emissions from formicine ants and automobile combustion were selected as two other potential sources for isotopic analysis. The HCOOH collected from auto exhaust was much more depleted in¹³C than the atmospheric samples, with a ¹³C of –28.0 and –48.6 from a leaded and unleaded automobile, respectively. Formicine ants, on the other hand, ranged from –17.2 to –20.6.     

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.     

珠江口盆地西江主洼油气差异分布机制

西江主洼是珠江口盆地一个低勘探程度洼陷，油气差异聚集特征明显，但其机理不清。本文在断陷盆地油气成藏理论指导下，利用研究区地质、地球物理和地球化学等资料，开展了烃源岩、断盖组合、储集体系和运聚模式等方面的研究。结果表明，裂陷期沉降、沉积中心有序迁移，造成主力烃源岩自东向西由文四段迁移至文三段、文一+二段，控制东、西部油气差异分布。恩平组区域性泥岩发育且晚期断裂缺乏，导致油气纵向上更易聚集于下构造层；区域泥岩减薄尖灭或晚期断裂切开盖层的区域，上构造层有一定油气分布。"源-汇"类型从宏观上控制储层优劣，影响下构造层油气富集程度；"仓储"运移是控制上构造层油气规模聚集的主要模式。下构造层古近系应作为重点部署方向，东部围绕文四段、西部围绕文三段、文一+二段烃源岩构成的含油气系统展开；上构造层勘探需关注珠海组，在隆起周边寻找具备"仓储"运移模式的有利区带。     

Diagenesis of vascular plant organic matter components during burial in lake sediments

Diagenetic changes are difficult to distinguish from variations in sources of organic matter to sediments. Organic geochemical comparisons of samples of wood, bark, and needles from a white spruce (Picea glauca) living today and one buried for 10,000 years in lake sediments have been used to identify the effects of diagenesis on vascular plant matter. Important biogeochemical changes are evident in the aged spruce components, even though the cellular structures of the samples are well preserved. Concentrations of total fatty acids dramatically diminish; unsaturated and shorter chainlength components are preferentially lost from the molecular distributions. Concentrations of total alcohols are similar in the modern and 10,000-year-old wood and bark but markedly lowered in the aged needles. Hydrocarbon concentrations and distributions show little diagenetic change in the 10,000-year-old plant materials. Cellulose components in the wood decrease relative to lignin components, although both types of materials remain in high concentration in comparison to other organic components. Aromatization of abietic acid proceeds more rapidly in buried spruce wood than in bark; retene is the dominant polyaromatic hydrocarbon in the aged wood. In contrast to the variety of changes evident in molecular compositions, neither ¹³C values nor C/N ratios differ significantly in the bulk organic matter of modern and aged spruce components.     

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.     

预测陕西关中地区需水量的改进GM(1,1)模型

需水量评价与预测是水资源规划与管理一项重要的研究内容。本文采用定额法计算需水量。通过对陕西关中地区需水量要素组成的分析,认为需水量要素属平稳时间序列,且一阶累加生成数据系列满足指数规律,符合灰色预测条件。为了提高GM(1,1)模型的精度,采用一种改变背景值的新方法,即:中心逼近方法。通过精度检验,中心逼近式GM(1,1)模型平均误差百分比、误差平方和分别比传统的GM(1,1)模型提高了0.147和1.579。用中心逼近式GM(1,1)模型预测需水量各要素近期和中长期值,经检验,其中非农业人口、农业人口、耕地面积、工业总产值预测模型满足一级模型,等级为良好。牲畜头数预测模型为不合格模型,分析其原因,主要是因为时间序列数据不完全符合指数规律。通过定额法计算,预计75%保证率时2005年和2010年关中地区工农业需水量分别占总需水量的92.21%和89.75%,生活需水量分别占7%和9.04%。     

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.