Long-term patterns in soil acidification due to pollution in forests of the Eastern Sudetes Mountains

Soil acidification was assessed in the Eastern Sudetes Mountains (Czech Republic) between 1941 and 2003, i.e. before and after the period of major industrial pollution (1950s-1990s). The twenty sites included in our study were distributed along a gradient of altitude ranging 1000 m. Values of pH have decreased in 80-90% of the pairs of samples after the six decades, on average by 0.7 for pH-H₂O and 0.6 for pH-KCl. Organic matter increased in the topsoil, probably reflecting a change in decomposition conditions. The most important finding is that the acidification varies along the joint gradient of altitude/tree layer composition, and displays a changing pattern in three soil horizons (A, B and C). Contrary to expectations, most acidified were soils in beech forests at lower elevations.     

The reactions of paraquat and divalent metal ions with humic acid: Factors influencing stoichiometry 2

Abstract

Laurentide humic acid has been titrated with paraquat and with selected divalent metal ions. In some cases, the humic acid was spiked with one cation before titration with another one. Several equivalence points were determined for the binding of the divalent cations, including paraquat. Three equivalence points agreed well with values predicted from the acidic properties of the humic acid. Eight independent experiments gave nine replicate values for an equivalence point that corresponds to 79.2 mole % of the total pairs of carboxyl groups. It is postulated that this represents a large molecular weight or structural fraction of the humic acid. The remaining 20.8 mole % can either bind one divalent cation to two carboxylate anions or bind one divalent cation to one carboxylate anion, with another anion providing for charge balance. Aggregation ‐ disaggregation and dissolution ‐precipitation phenomena may determine which case prevails, and they in turn are sensitive to the chemical compositions of samples. It should be possible to develop analytical chemical methods for characterizing the stoichiometric properties of humic acid samples.     

Mathematical prediction of imidacloprid persistence in two Croatian soils with different texture,organic matter content and acidity under laboratory conditions

In the present laboratory study, persistence of imidacloprid (IMI) as a function of initial insecticide concentration and soil properties in two Croatian soils (Krk sandy clay and Istria clay soils) was studied and described mathematically. Upon fitting the obtained experimental data for the higher concentration level (5 mg/kg) to mathematical models, statistical parameters (R ², scaled root mean squared error and χ ² error) indicated that the single first-order kinetics model provided the best prediction of IMI degradation in the Krk sandy clay soil, while in the Istria clay soil biphasic degradation was observed. At the lower concentration level (0.5 mg/kg), the biphasic models Gustafson and Holden models as well as the first-order double exponential model fitted the best experimental data in both soils. The disappearance time (DT₅₀) values estimated by the single first-order double exponential model (from 50 to 132 days) proved that IMI can be categorized as a moderately persistent pesticide. In the Krk sandy clay soil, resulting DT₅₀ values tended to increase with an increase of initial IMI concentration, while in the Istria clay soil, IMI persistence did not depend on the concentration. Organic matter of both experimental soils provided an accelerating effect on the degradation rate. The logistic model demonstrated that the effect of microbial activity was not the most important parameter for the biodegradation of IMI in the Istria clay soil, where IMI degradation could be dominated by chemical processes, such as chemical hydrolysis. The results pointed that mathematical modeling could be considered as the most convenient tool for predicting IMI persistence and contributes to the establishment of adequate monitoring of IMI residues in contaminated soil. Furthermore, IMI usage should be strictly controlled, especially in soils with low organic matter content where the risk of soil and groundwater contamination is much higher due to its longer persistence and consequent leaching and/or moving from soil surface prior to its degradation.     

Effects of pollution on humic substances

Abstract

To assess effects of industrial and environmental pollution on analytical characteristics of humic substances, we isolated humic acids (HA's) and fulvic acids (FA's) from unpolluted and polluted soils and sediments. Following purification, the HA's and FA's were characterized by elemental (C, H, O, N, S) and functional group (CO₂H, phenolic OH, total acidity) analyses, infrared (IR) spectrophotometry, differential thermal analysis (DTA) and by metal (Fe, Al, Cu, Mn, Pb, Ni, Co, Zn, Cr, Cd, Hg, Ca and Mg) analyses. Si was also determined in all samples.

Polluted HA's and FA's contained more N and S but less 0 and were richer in all metals and Si than were unpolluted ones. IR spectra showed that polluted humic materials were enriched in COO^‐ groups, secondary non‐cyclic amides and possible also in SO₃H groups. DTA curves indicated that polluted HA's and FA's were more thermostable than unpolluted HA's and FA's. Unusually high N, S, Cu, Cr, Zn and Hg contents of humic materials appear to be useful indicators of soil and sediment pollution.     

石墨炉原子吸收法测定降水中重金属

建立了石墨炉原子吸收测定大气降水中Pb、Mn、Fe、Zn、Cu、Cr、Cd的方法，优化了试验条件。方法线性良好，7种元素的检出限为0．54μg／L-2．2μg／L，RSD为3．0％-7．3％，加标回收率为101％-105％，实际降水样品的测定结果令人满意。     

The effect of improved nowcasting of precipitation on air quality modeling

The predictive potential of air quality models and thus their value in emergency management and public health support are critically dependent on the quality of their meteorological inputs. The atmospheric flow is the primary cause of the dispersion of airborne substances. The scavenging of pollutants by cloud particles and precipitation is an important sink of atmospheric pollution and subsequently determines the spatial distribution of the deposition of pollutants. The long-standing problem of the spin-up of clouds and precipitation in numerical weather prediction models limits the accuracy of the prediction of short-range dispersion and deposition from local sources. The resulting errors in the atmospheric concentration of pollutants also affect the initial conditions for the calculation of the long-range transport of these pollutants. Customary the spin-up problem is avoided by only using NWP (Numerical Weather Prediction) forecasts with a lead time greater than the spin-up time of the model. Due to the increase of uncertainty with forecast range this reduces the quality of the associated forecasts of the atmospheric flow.In this article recent improvements through diabatic initialization in the spin-up of large-scale precipitation in the Hirlam NWP model are discussed. In a synthetic example using a puff dispersion model the effect is demonstrated of these improvements on the deposition and dispersion of pollutants with a high scavenging coefficient, such as sulphur, and a low scavenging coefficient, such as cesium-137. The analysis presented in this article leads to the conclusion that, at least for situations where large-scale precipitation dominates, the improved model has a limited spin-up so that its full forecast range can be used. The implication for dispersion modeling is that the improved model is particularly useful for short-range forecasts and the calculation of local deposition. The sensitivity of the hydrological processes to proper initialization implies that the spin-up problem may reoccur with changes in the model and increased model resolution. Spin-up should be an ongoing concern for atmospheric modelers.     

近20年来太湖流域典型地区土壤酸度的时空变异特征

以第二次土壤普查资料和近期采样分析数据为基础，运用地统计学方法研究了太湖流域典型区域土壤酸度的时空变异特征。结果表明，研究区域土壤总体上呈酸化趋势，表现在绝大部分(超过85%的面积)土壤的pH值发生不同程度的下降，且平均降幅达0.56个pH单位。同第二次土壤普查时期相比，土壤pH值空间变异的自相关性显著增强，但空间自相关距离明显减小，表明土壤pH值空间分布格局趋向复杂化，岛状分布更为明显。化学肥料的连年大量施用和工业污染物的长期排放是导致土壤趋向酸化和土壤酸度空间分布格局发生变化的主要原因。     

Chemical characteristics of precipitation at metropolitan Newark in the US East Coast

To investigate the chemical characteristics of precipitation in the polluted coastal atmosphere, a total of 46 event-based precipitation samples were collected using a wet-only automatic precipitation collector from September 2006 to October 2007 at metropolitan Newark, New Jersey in the US East Coast. Samples were analyzed by ion chromatography for the concentrations of major inorganic ions (Cl⁻, NO₃⁻, SO₄²⁻, F⁻, NH₄⁺, Ca²⁺, Mg²⁺, Na⁺, K⁺) and organic acid species (CH₃COO⁻, HCOO⁻, CH₂(COO)₂²⁻, C₂O₄²⁻). Selected trace metals (Sb, Pb, Al, V, Fe, Cr, Co, Ni, Cu, Zn, Cd) in samples were determined by ICPMS. Mass concentration results show that SO₄²⁻ was the most dominant anion accounting for 51% of the total anions, controlling the acidity of the precipitation. NH₄⁺ accounted for 48.6% of the total cations, dominating the precipitation neutralization. CH₃COO⁻ and HCOO⁻ were the two dominant water-soluble organic acid species, accounting for 42% and 40% of the total organic acids analyzed, respectively. Al, Zn and Fe were the three major trace metals in precipitation, accounting for 34%, 27%, and 25% of the total mass of metals analyzed. The pH values in precipitation ranged from 4.4 to 4.9, indicating an acidic nature. Enrichment Factor (EF) Analysis showed that Na⁺, Cl⁻, Mg²⁺ and K⁺ in the precipitation were primarily of marine origin, while most of the Fe, Co and Al were from crust sources. Pb, V, Cr, Ni were moderately enriched with EFs ranging 43–410, while Zn, Sb, Cu, Cd and F⁻ were highly enriched with EFs > 700, indicating significant anthropogenic influences. Factor analysis suggests 6 major sources contributing to the observed composition of precipitation at this location: (1) nitrogen-enriched soil, (2) secondary pollution processes, (3) marine sources, (4) incinerations, (5) oil combustions, and (6) malonate–vanadium enriched sources. To further explore the source–precipitation event relationships and seasonality, cluster analysis was performed for all precipitation events. Results show that about half of the precipitation events were characterized by mixed sources. Significant influences of nitrogen-enriched soil and marine sources were associated with precipitation events in spring and autumn, while secondary pollution processes, incineration and oil combustion contributed greatly in summer.     

关于《酸沉降监测技术规范》(HJ/T165-2004)中的几处修正意见

介绍了降水监测数据的阴、阳离子平衡和电导率平衡检验的计算方法,对国家环保总局发布的<酸沉降监测技术规范>(HJ/T165-2004)中公式存在的几个不妥之处提出修正意见.     

我国垃圾焚烧飞灰性质及其重金属浸出特性分析

调查分析了我国12个垃圾焚烧飞灰样品的性质和重金属浸出规律.结果表明,飞灰的主要组成元素有Si、Ca、Al、Fe、K、Na、Cl 等,除1个样品外,飞灰样品中的重金属元素含量均在0 .5%～3 .0%范围内.由此可见焚烧飞灰具有较大的环境风险,必须按危险废物进行安全管理.应用单批次浸出程序检测结果表明,美国EPA的毒性浸出程序（TCLP）和我国固体废物浸出毒性鉴别程序（GB 5086 .1-1997）对焚烧飞灰中的重金属浸出率偏低,且二者对飞灰危险性评估的差异较大,这主要是受二者不同的浸出液最终的pH值所影响.常规酸中和容量（GANC）浸出试验结果表明,飞灰中重金属的浸出主要受浸出液的最终pH值影响,而该pH值取决于飞灰中碱性物质与浸取剂酸度二者间的相互作用.通过对不同类别程序的浸出过程分析发现,在相同浸取液作用下,单批次式浸出程序的静态平衡终点与连续过流式浸出程序的平衡终点存在较大差异,有必要结合我国飞灰特点和实际处置场景,建立适用于焚烧飞灰的单批次式毒性浸出试验程序,避免对飞灰危险性识别的不足和管理的失控.