菜园土壤中的铜及其与土壤有机碳的关系

通过野外调查与室内分析相结合的方法研究了杭州市郊主要菜园土壤中铜的状况,并对其与土壤有机碳的关系作了探讨.取样分析结果表明,调查区域菜园土壤全铜含量在4.3×10-6～205.5×10-6之间,平均为(43.6±36.7)×10-6,有效铜含量在0.17×10-6～6.18×10-6之间,平均为(2.70±1.46)×10-6.同时还发现,菜园土壤有效铜含量与全铜含量呈极显著正相关,相关系数为0.717**(n=45,P=0.01,下同),据此认为菜园土壤有效铜的供给是以全铜量为基础的.相关分析还得出,全铜含量与总有机碳和易氧化碳含量均呈极显著正相关,相关系数分别为0.695**和0.594**;有效铜含量也与总有机碳和易化有机碳含量呈极显著正相关,相关系数分别为0.666**和0.557**,这表明施用有机肥料可能是菜园土壤铜营养的重要来源之一.另外,菜园土壤铜的有效性也有随土壤总有机碳和易氧化有机碳含量的提高而增大的趋势,这对一般情况下提高土壤的供铜强度是有益的.但是,倘若土壤中已积累了过量的铜,则有可能加剧铜的毒害,蔬菜生产和菜园土壤管理中都应予以足够的重视.     

Influence of nitrogen speciation on the TDN measurement in fresh waters by high temperature catalytic oxidation and persulfate digestion

Analytical methodologies for the determination of total dissolved nitrogen (TDN) in waters are based on a conversion step able to transform selectively all the nitrogen species into a compound that is then quantified. A crucial requirement to meet accuracy is the quantitative recovery of all organic and inorganic nitrogen species during the conversion step. In this work, the N recoveries of two widely employed methodologies that use different conversion steps (high temperature catalytic oxidation (HTCO) and persulfate digestion (PD)) were assessed on a set of organic nitrogen compounds, representative of the structures of both dissolved organic matter (DOM) and anthropogenic contaminants. Low recoveries are due to poor selectivity during the conversion step, with the formation of nitrogen compounds other than nitrogen oxide (HTCO) and nitrate (PD). The results show that in many instances the TDN measurements give systematically low results depending on N speciation. PD could give lower results than HTCO even for samples containing only DOM of biological origin. In particular (i) low N recovery was always observed with compounds having two or more contiguous N atoms; (ii) the HTCO method is very effective for TDN quantification in the presence of s-triazine rings while PD method did not yield satisfactory N recovery; (iii) a full N recovery was observed with compounds having amido or amino groups or nitrogen atoms in imidazole, indole and pyrimidine rings; and (iv) the N recoveries for purine derivatives are almost complete with HTCO, but give systematically low results by PD.

Finally, the estimation of dissolved organic nitrogen (DON) fluxes and pools from TDN measurements can be affected by uncertainties larger than previously thought as a consequence of (i) the lower N recovery for some nitrogen compounds and (ii) the differences in the N recovery as a function of the adopted analytical methods.     

Some theoretical and practical aspects in the separation of humic substances by combined liquid chromatography methods

Permanent need to understand nature, structure and properties of humic substances influences also separation methods that are in a wide scope used for fractionation, characterization and analysis of humic substances (HS). At the first glance techniques based on size-exclusion phenomena are the most useful and utilized for relating elution data to the molecular mass distribution of HS, however, with some limitations and exceptions, respectively, in the structural investigation of HS. The second most abundant separation mechanism is reversed-phase based on weak hydrophobic interactions beneficially combined with the step gradients inducing distinct features in rather featureless analytical signal of HS. Relatively great effort is invested to the developments of immobilized-metal affinity chromatography mimicking chelate-forming properties of HS as ligands in the environment. Surprisingly, relatively less attention is given to the ion-ion interactions based ion-exchange chromatography of HS. Chromatographic separation methods play also an important role in the examination of interactions of HS with pesticides. They allow us to determine binding constants and the other data necessary to predict the mobility of chemical pollutants in the environment. HS is frequently adversely acting in analytical procedures as interfering substance, so more detailed information is desired on manifestation of its numerous properties in analytical procedures. The article topic is covered by the review emphasizing advances in the field done in the period of last 10 years from 2000 till 2010.