不同阻垢剂对方解石和磷酸钙表面电位的影响

采用微电泳法考察了１５种阻垢剂对方解石和磷酸钙颗粒表面电位的影响。实验结果表明,在各种药剂中,丙烯酸／２ 丙烯酰胺基 ２ 甲基丙磺酸／次磷酸调聚物对难溶盐表面电位影响最大,乙二胺四乙酸二钠盐的影响最小。乙二胺四甲叉膦酸的溶垢能力和对表面电位的影响都较强。各种药剂对两种难溶盐表面电位影响的排序差异不显著。根据配位化学和表面化学原理解释了实验结果。     

Comment on: Mass Fractions of Forty‐Six Major and Trace Elements,Including Rare Earth Elements,in Sediment and Soil Reference Materials Used in Environmental Studies. Fiket et al. (2017), Geostandards and Geoanalytical Research, 41, 123–135

This paper is intended to be a constructive discussion of Fiket et al. (2017, Geostandards and Geoanalytical Research , 41 , 123–135), who dealt with the determination of major, trace and rare earth elements in several sediment and soil certified reference materials. In the present author's view, the paper by Fiket et al. (2017) suffers from a lack of reference to several publications in which somewhat similar results had already been reported. The present contribution therefore provides a comparison of previously published results with those of Fiket et al. for the CRMs soil NCS DC 77302 (GBW 07410), stream sediment NCS DC 73309 (GBW 07311), marine sediments MESS‐3 and NCS DC 75301 (GBW 07314) and estuarine sediment IAEA‐405. It is argued that this fuller consideration (a) allows critical evaluation of the quality of the results presented by Fiket et al. and (b) highlights the advantages of their work. Finally, attention is drawn to the (possible or real) problems that can arise during simultaneous determination of multiple trace elements.     

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.     

The Removal of Dissolved Metals by Hydroxysulphate Precipitates during Oxidation and Neutralization of Acid Mine Waters, Iberian Pyrite Belt

This study examines the removal of dissolved metals during the oxidation and neutralization of five acid mine drainage (AMD) waters from La Zarza, Lomero, Esperanza, Corta Atalaya and Poderosa mines (Iberian Pyrite Belt, Huelva, Spain). These waters were selected to cover the spectrum of pH (2.2–3.5) and chemical composition (e.g., 319–2,103 mg/L Fe; 2.85–33.3 g/L SO₄⁼) of the IPB mine waters. The experiments were conducted in the laboratory to simulate the geochemical evolution previously recognized in the field. This evolution includes two stages: (1) oxidation of dissolved Fe(II) followed by hydrolysis and precipitation of Fe(III), and (2) progressive pH increase during mixing with fresh waters. Fe(III) precipitates at pH < 3.5 (stages 1 and 2) in the form of schwertmannite, whereas Al precipitates during stage 2 at pH 5.0 in the form of several hydroxysulphates of variable composition (hydrobasaluminite, basaluminite, aluminite). During these stages, trace elements are totally or partially sorbed and/or coprecipitated at different rates depending basically on pH, as well as on the activity of the SO₄⁼ anion (which determines the speciation of metals). The general trend for the metals which are chiefly present as aqueous free cations (Pb²⁺, Zn²⁺, Cu²⁺, Cd²⁺, Mn²⁺, Co²⁺, Ni²⁺) is a progressive sorption at increasing pH. On the other hand, As and V (mainly present as anionic species) are completely scavenged during the oxidation stage at pH < 3.5. In waters with high activities (> 10⁻¹) of the SO ₄⁼ ion, some elements like Al, Zn, Cd, Pb and U can also form anionic bisulphate complexes and be significantly sorbed at pH < 5. The removal rates at pH 7.0 range from around 100% for As, V, Cu and U, and 60–80% for Pb, to less than 20% for Zn, Co, Ni and Mn. These processes of metal removal represent a significant mechanism of natural attenuation in the IPB.     

盐湖相低熟油脂肪酸的组成与分布特征

对泌阳凹陷碱性盐湖相、舞阳凹陷盐湖相、襄城凹陷膏盐湖相、南阳凹陷淡水湖相低熟油脂肪酸组成和分布特征进行了分析与研究。结果表明这些不同盐湖相的低熟原油的脂肪酸为丰度不同的饱和正构酸、不饱和正构酸、少量异构酸、类异戊二烯酸及脂肪酸乙酯系列化合物。脂肪酸的组成和分布反映了原始有机质的来源。     

磺基水杨酸光度法连续测定岩石中的铁和钛

本文提出用磺基水杨酸(SSA)作显色剂,在不同pH值和同一波长下.于一分试液中连续测定铁和钛的分析方法。测定波长为420nm,测铁的pH值为8—11,Fe量在0—10μg/ml范围内服从比尔定律;测钛的pH值为2,TiO_2量在0—14μg/ml范围内服从比尔定律。     

CdTe量子点荧光猝灭法测定赤泥中痕量镍

Cd Te量子点具有荧光强度高和稳定性好的优点,应用Cd Te量子点荧光猝灭法分析基体复杂的样品,需要有效分离对测定干扰的金属元素和高效富集待测元素。本文以巯基乙酸(TGA)作稳定剂,采用水相合成法制备了巯基乙酸修饰的Cd Te量子点,基于镍离子在p H=10.0硼砂缓冲溶液中对Cd Te量子点的荧光具有较强猝灭作用,建立了一种测定赤泥中痕量镍的荧光光度方法。荧光猝灭反应的最佳实验条件为:Cd Te量子点的浓度3.0×10-4mol/L,反应温度为室温,反应时间10 min,在此条件下镍离子浓度在2.0×10-7~7.8×10-5mol/L范围内与Cd Te量子点的相对荧光强度呈良好的线性关系;方法检出限为1.5×10-7mol/L。本方法针对Fe3+、Co2+、Cu2+等主要基体金属元素允许量低的问题,采用25%的2-羟基-4-仲辛氧基二苯甲酮肟(N530)磺化煤油萃取回收滤液中的Ni2+,镍回收率达到99%以上;赤泥中痕量镍的测定结果与催化光度法相符,加标回收率为98.3%-104.2%。     

Humic Ion-Binding Model VI: An Improved Description of the Interactions of Protons and Metal Ions with Humic Substances

Humic Ion-Binding Model VI, a discrete site/electrostatic model of the interactions of protons and metals with fulvic and humic acids, is applied to 19 sets of published data for proton binding, and 110 sets for metal binding. Proton binding is described with a site density, two median intrinsic equilibrium constants, two parameters defining the spread of equilibrium constants around the medians, and an electrostatic constant. Intrinsic equilibrium constants for metal binding are defined by two median constants, log K_MA and log K_MB, which refer to carboxyl and weaker-acid sites respectively, together with a parameter, LK₁, defining the spreads of values around the medians. A further parameter, LK₂, takes account of small numbers of strong binding sites. By considering results from many data sets, a universal average value of LK₁ is obtained, and a correlation established between log K_MB and log K_MA. In addition, a relation between LK₂ and the equilibrium constant for metal-NH₃ complexation is tentatively suggested. As a result, metal-binding data can be fitted by the adjustment of a single parameter, log K_MA. Values of log K_MA are derived for 22 metal species. Model VI accounts for competition and ionic strength effects, and for proton-metal exchange.     

Statistical evaluation of tectonomagmatic discrimination diagrams for granitic rocks and proposal of new discriminant-function-based multi-dimensional diagrams for acid rocks

The four tectonic discrimination diagrams of Pearce et al. [Journal of Petrology, v. 25, p. 956–983] for granitic rocks were first evaluated using the literature cited by these authors as well as from our new database. The first diagram (Y?Nb) cannot discriminate volcanic-arc and collision settings. Both Y?Nb and Yb?Ta diagrams have an overlapping field for within-plate and ocean-ridge granitoids. The remaining two diagrams (Y?+?Nb?Rb and Yb?+?Ta?Rb) use a mobile element (Rb) in their y-axis. Although these diagrams successfully discriminate volcanic-arc and within-plate granites, they perform less well for collision tectonics. Besides, felsic or acid rocks are scarce in ocean-ridge settings, which limits the usefulness of these diagrams for this geological environment. Therefore, using an extensive database, we proposed a set of five new discriminant-function-based multi-dimensional diagrams for acid magmas from four tectonic settings (island arc, continental arc, continental rift, and collision). The very similar tectonic settings of island and continental arcs are discriminated for the first time. These diagrams are based on correct statistical treatment of compositional data, because they use natural logarithm transformation of major-element ratios and linear discriminant analysis (LDA). The use of discordant outlier-free samples prior to LDA improved the success rates by about 3–5%. Success rates of these diagrams as inferred from a testing set were between 76% and 88% for island arc, 60% and 92% for continental arc, and 72% and 84% for both continental rift and collision settings. Finally, application of these new diagrams to case studies not compiled in our initial database used for constructing these diagrams provided the following results: a collision setting for the Himalayas at about 30 Ma; an island arc setting for Quaternary acid rocks from geothermal boreholes in El Salvador; an island- or continental-arc setting for northern Italy at 35–52 Ma; a continental-arc setting for the Italy–Austria border at about 30 Ma; either a rift or a collision setting for northern Nigeria at about 164 Ma; a collision setting for central Nigeria at about 144 Ma and for the Cretaceous Masirah ophiolites of Oman; and an island arc setting for the Cretaceous Semail ophiolites of Oman. In spite of the relative mobility of major elements, these applications suggest utility of the new discrimination diagrams for all four tectonic settings.     

Simulation of the dissolution of weathered versus unweathered limestone in carbonic acid solutions of varying strength

A simulation was undertaken within a climatic chamber to investigate limestone dissolution under varied carbonic acid (H₂CO₃) strengths as a possible analogue for future increases in atmospheric CO₂ arising from global warming. Twenty‐eight samples cut from a block of Bath (Box Hill) limestone from Somerville College, Oxford, which had been removed during restoration after 150 years in an urban environment, were weighed and placed in closed bottles of thin plastic containing varying concentrations of H₂CO₃. Half of the stone samples were derived from exposed surfaces of the stone block (weathered) while the others were obtained from the centre of the block on unexposed surfaces (unweathered). The purpose of this was to compare dissolution of previously weathered versus unweathered surfaces in strong (pH 4·73) versus weak (pH 6·43) solutions of H₂CO₃. A temperature of c. 19 °C was maintained within the chamber representing a plausible future temperature in Oxford for the year 2200 given current warming scenarios. The simulation lasted 25 days with a few stone samples being removed midway. Stone samples show reduced weight in all cases but one. There was greater dissolution of stone samples in a strong H₂CO₃ solution as conveyed by higher concentrations of total hardness and Ca²⁺ in the water samples as well as enhanced microscopic dissolution features identified using SEM. The simulation confirms that enhanced atmospheric CO₂ under global warming, given adequate moisture, will accelerate dissolution rates particularly of newly replaced limestone building stones. However, previously weathered surfaces, such as those on historical stone exposed for a century or more, appear to be less susceptible to the effects of such increased rainfall acidity. Conservation techniques which remove weathered surfaces, such as stone cleaning, may accelerate future decay of historical limestone structures by increasing their susceptibility to dissolution. Copyright © 2006 John Wiley & Sons, Ltd.