Effects of Soil Composition on Zn Speciation in Drainage Waters from Agricultural Soils

The influence of Zn speciation on Zn transport by drainage from different soils to surface water is examined in a stream catchment in an agricultural area. Drainage waters were collected from two types of soils, a mineral soil (MS) and a soil rich in organic matter (OS) by means of artificial drainage pipes. The speciation of dissolved Zn in the stream and the drainage waters was determined using ligand-exchange and voltammetry. About 50–95% of dissolved Zn is bound in strong complexes, and the free Zn²⁺ ion concentration is in the range of 1–16% of dissolved Zn. A substantial part of Zn is present in weaker organic or inorganic complexes. The simulated Zn speciation using the WHAM VI model is compared to the determined speciation. Free Zn²⁺ concentrations predicted by the WHAM VI model are generally higher than the analytically determined free Zn²⁺, but are mostly within the same order of magnitude. Effects of different soil organic matter content on Zn speciation and transport are discussed. Zn speciation in the drainage at the OS site is influenced by the distribution of organic matter between the solid and solution phase. The abundant organic Zn complexes in solution contribute to facilitate Zn transport from soil into surface waters, through the drainage at the OS site. Drainage from the OS site contributes about twice as much Zn input to the receiving water as the MS soil, as related to specific area. The mineral soil contains much lower organic matter, and a part of Zn bound with inorganic phases can hardly be released by dissolved organic ligands, leading to much higher Zn retention at the MS site.     

Comparison of atmospheric forcing in four sub-arctic seas

A comparative analysis was conducted on climate variability in four sub-arctic seas: the Sea of Okhotsk, the Bering Sea shelf, the Labrador Sea, and the Barents Sea. Based on data from the NCEP/NCAR reanalysis, the focus was on air–sea interactions, which influence ice cover, ocean currents, mixing, and stratification on sub-seasonal to decadal time scales. The seasonal cycles of the area-weighted averages of sea-level pressure (SLP), surface air temperature (SAT) and heat fluxes show remarkable similarity among the four sub-arctic seas. With respect to variation in climate, all four seas experience changes of comparable magnitude on interannual to interdecadal time scales, but with different timing. Since 2000 warm SAT anomalies were found during most of the year in three of the four sub-arctic seas, with the exception of the Sea of Okhotsk. A seesaw (out of phase) pattern in winter SAT anomalies between the Labrador and the Barents Sea in the Atlantic sector is observed during the past 50 years before 2000; a similar type of co-variability between the Sea of Okhotsk and the Bering Sea shelf in the Pacific is only evident since 1970s. Recent positive anomalies of net heat flux are more prominent in winter and spring in the Pacific sectors, and in summer in the Atlantic sectors. There is a reduced magnitude in wind mixing in the Sea of Okhotsk since 1980, in the Barents Sea since 2000, and in early spring/late winter in the Bering Sea shelf since 1995. Reduced sea-ice areas are seen over three out of four (except the Sea of Okhotsk) sub-arctic seas in recent decades, particularly after 2000 based on combined in situ and satellite observations (HadISST). This analysis provides context for the pan-regional synthesis of the linkages between climate and marine ecosystems.     

HNO3-HClO4-原子吸收分光光度法测定海洋生物体中Cu,Pb,Zn,Cd,Cr

参考《海洋监测规范第6部分:生物体分析》(GB17378.6-1998)的规范方法,采用单一HNO3-HClO4常压方法消化贻贝成分分析分析标准物质(GBW08571)。取样量为0.500g时,在加热温度为160℃～210℃,加入10mL HNO3、2mLHClO4,加盖加热7h左右,最后的样品消化液赶酸赶净的条件下,样品消化液直接以原子吸收分光光度计测定,其中Cu,Pb,Zn,Cd,Cr的测定值都在标准值范围之内。并着重对比温度对消化效果的影响以及Cu,Cd以火焰法与无火焰法测定的差别。     

岩溶区与非岩溶区不同土地利用方式下土壤Zn元素形态分析

本文采用连续提取法,对岩溶区与非岩溶区农田和林地两种土地利用形式下土壤中Zn元素形态进行了分级提取。测定结果表明,土壤中Zn元素主要以残渣态(占总量68. 5%～ 85. 0% )存在。此外,岩溶区农田、林地石灰土中Zn元素相对活泼态,即离子交换态(包括水溶态)、碳酸盐结合态、腐殖酸结合态(松结有机结合态)的含量均比非岩溶区对应的要低,而相对稳定态,即铁锰氧化物结合态、强有机结合态(包括部分硫化物态)的含量均比非岩溶区相对应的要高,残渣态含量与相对稳定态具有相同的趋势。这意味着岩溶土壤地球化学环境对土壤Zn的迁移、富集、形态转换具有明显的影响。长期耕种下岩溶区和非岩溶区土壤均会出现缺Zn状况,岩溶区情况更为严重。而适宜的土壤改良措施,可望提高土壤有效Zn形态的含量。      

Combined Separation of Cu,Fe and Zn from Rock Matrices and Improved Analytical Protocols for Stable Isotope Determination

Isotope ratios of heavy elements vary on the 1/10000 level in high temperature materials, providing a fingerprint of the processes behind their origin. Ensuring that the measured isotope ratio is precise and accurate depends on employing an efficient chemical purification technique and optimised analytical protocols. Exploiting the disparate speciation of Cu, Fe and Zn in HCl and HNO₃, an anion exchange chromatography procedure using AG1‐×8 (200–400 mesh) and 0.4 × 7 cm Teflon columns was developed to separate them from each other and matrix elements in felsic rocks, basalts, peridotites and meteorites. It required only one pass through the resin to produce a quantitative and pure isolate, minimising preparation time, reagent consumption and total analytical blanks. A ThermoFinnigan Neptune Plus MC‐ICP‐MS with calibrator‐sample bracketing and an external element spike was used to correct for mass bias. Nickel was the external element in Cu and Fe measurements, while Cu corrected Zn isotopes. These corrections were made assuming that the mass bias for the spike and analyte element was identical, and it is shown that this did not introduce any artificial bias. Measurement reproducibilities were ± 0.03‰, ± 0.04‰ and ± 0.06‰ (2s) for δ⁵⁷Fe, δ⁶⁵Cu and δ⁶⁶Zn, respectively.     

Zn(II) Ion Biosorption onto Surface of Eucalyptus Leaf Biomass: Isotherm,Kinetic, and Mechanistic Modeling

Bioremediation of Zn(II) by biosorption across aqueous phase on to surface of eucalyptus leaf powder has been investigated in present research work. The adsorptive potential of eucalyptus leaf powder was evaluated as function of pH, temperature, contact time, agitation rate and particle size. Maximum metal ion uptake and percentage removal capacity of eucalyptus leaf powder were 23.5 mg g⁻¹ and 94%, respectively, at optimized pH 5, 20 ± 1°C, contact time 6 h, particle size 0.5 mm and agitation rate 200 rpm. The biomass surface analysis revealed the fact that the biomass surface was heterogeneous and porous in nature. The functional groups like amine, amide, carboxyl, hydroxyl, and methyl groups, significantly important for metal ion binding were present on biomass surface in tremendous amount. Additionally, the Fourier transformation IR spectrum analysis of acid and base activated eucalyptus leaf biomass ruled out all the possibilities of the presence of surface functional groups mentioned above. The reaction rate was studied by applying two rate limiting models pseudo first and pseudo second order. Pseudo second order model was found to be more suitable (R² = 0.998) in comparison to pseudo first order (R² = 0.724). Adsorption equilibrium of batch stirred reaction data fitting shows the dominance of Langmuir isotherm (R² = 0.99) against Freundlich isotherm (R² = 0.887) model with equipartitional involvement of both film and intra particle diffusion as rate limiting steps at differential status of contact time.     

Nitrogen isotope ratios of nitrate as a clue to the origin of nitrogen on the Pacific coast of Japan

To clarify the sources and transformation of NO₃⁻ on the Pacific coast of Japan, observations over the continental shelf were conducted during the summer in 2005 and 2006 when the Kuroshio flowed close to and away from the coastal area, respectively. Below the halocline, there are two prominent salinity peaks that originated in two different waters. In the subsurface layer, the salinity maximum (S_max) was indicative of the Kuroshio Water (KW), while the salinity minimum (S_min) in the middle layer at ∼400 m depth was indicative of the North Pacific Intermediate Water (NPIW). δ¹⁵N_NO3 ranged from 4.1‰ to 5.1‰ with a mean of 4.8±0.4‰ in the deeper water around S_min. Below 50 m depth over the shelf break, δ¹⁵N_NO3 values (3.1±0.8‰ in 2005 and 4.6±0.3‰ in 2006) clearly increased as contribution of NPIW increased in 2006. On the contrary, subsurface δ¹⁵N of NO₃⁻ values (−1.1±0.1‰) remained unchanged in both years, although the contribution of the KW to the subsurface water changed significantly. This suggests that the source of NO₃⁻ has little effect on the δ¹⁵N of NO₃⁻ in this layer. The negative δ¹⁵N values also coincided with the base of the chlorophyll maximum layer suggesting that these isotopic signals must be evidence of active nitrification in the upper layer.     

Isotopic temporal and spatial variations of tropical rivers in Thailand reflect monsoon precipitation signals

Stable isotopic compositions (δ¹⁸O and d-excess) from 25 rivers in Thailand were analysed monthly during 2013–2015. Results indicated that monsoon precipitation fundamentally influences the river isotopes. The overland flow supplied from monsoon precipitation and human-altered flow regimes produces considerable isotopic variability. Spatial and temporal variations were observed among four principal geographical regions. The seasonality of monsoon precipitation in mountainous Thailand produced large variations in isotopic compositions because most rainfall occurred during the southwest monsoon, and dry conditions prevailed during the northeast monsoon. The northern and northeastern regions are mountainous, highland areas. Low δ¹⁸O values were found in these regions, likely because of altitude effects on precipitation. Conversely, monsoonal precipitation continually supplies rivers in southern Thailand all year round, producing higher and more consistent δ¹⁸O values than in the other regions. The Chao Phraya plain in the central region experienced enrichment of δ¹⁸O river runoff related to evaporation in irrigation systems. Larger catchment areas and longer residence times resulted in more pronounced evaporation effects, producing lower values of d-excess and local river water line slopes compared with precipitation. The isotopic differences between river waters and precipitation were utilized to determine river recharge elevations and water transit time. The methods presented here can be used to explore hydrological interactions in other tropical river basins.     

澜沧大黑山铅锌多金属矿火山地质作用与成矿

大黑山矿属老厂矿之南延,两者有较多相似处。而火山地质作用与成矿关系密切,控制成矿空间和时间,亦是成矿物质及热力主要来源。进一步工作将可扩大远景。     

盐生荒漠土壤水稳定氢、氧同位素组成季节动态

对准噶尔盆地东南缘降水和土壤水稳定氢、氧同位素组成（δ¹⁸O和δD）进行了测定,分析了降水中δ¹⁸O和δD值的季节变化规律,表层土壤水中δ¹⁸O和δD值对降水脉冲的动态响应以及不同深度土壤水中δ¹⁸O和δD值的变化特征。结果表明：该区域大气降水线为δD=7.691δ¹⁸O+4.606;降水与表层土壤水中δ¹⁸O和δD值表现出明显的季节变化特征;表层土壤水中δ¹⁸O和δD值、质量含水量对降水脉冲响应显著,且不同量级的降水导致不同程度的响应。利用LSD法对0~300 cm土层内土壤水中δ¹⁸O和δD值进行多重比较分析,可将土壤在垂直方向上分为3层,表层（0~50 cm）土壤水分活跃,稳定同位素值随深度的增加而迅速减小;中间层（50~180 cm）土壤水分相对活跃,既受到降水入渗和蒸发作用的影响,也有地下水的补给;深层（180~300 cm）水分来源稳定,土壤水中δ¹⁸O和δD值基本不变。