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.     

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.     

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.     

Study of sorption kinetics of some ionic liquids on different soil types

In the present contribution sorption kinetics experiments under static conditions were utilized in three selected ionic liquids cations (1-ethyl-3-methylimidazolium, 1-butyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium chlorides) study with five type of soil, differing in total organic carbon (TOC) content. The experimental results indicate the sorption capacity growth with increase in TOC content and hydrophobicity of ionic liquid cation. The obtained kinetic sorption parameters as well as distribution coefficients (K_d) were used to estimate the sorption properties of the soil types towards the ionic liquids in question. The Gibbs free energy values indicate that ionic liquid cations sorption on soils could be generally considered as a physical adsorption with exothermic effect. But the values of −dG for studied cations sorption on soil with very high of TOC content in soil (45%) may testify to nature of chemical adsorption. Sorption of the analyzed compounds occurs probably by means of hydrogen bonds, electrostatic and π  π interaction with the organic matter and the clay minerals of the soils.     

华山地区PM2.5中无机离子垂直分布特征

2016年夏季在华山山腰及山脚设两个采样点（垂直高程相差约700 m）,运用大流量采样器进行每4 h 1次PM_2.5样品采集,对其无机离子进行分析,探讨其浓度、组成、垂直变化、日变化及酸度的特征.结果表明：采样期间,华山山腰及山脚的PM_2.5分别为：（46.9±38.2）μg·m^-3和（76.0±44.3）μg·m^-3,PM_2.5中无机离子分别为：（16.6±15.7）μg·m^-3和（24.0±15.0）μg·m^-3.两个点位无机离子浓度依次为：SO₄^2- > NO₃^- > NH₄⁺ > Ca²⁺.SO₄^2-、NO₃^-、NH₄⁺为主要组分,占华山山腰及山脚大气PM_2.5总离子质量浓度的89%和85%.线性回归分析显示：PM_2.5中的NH₄⁺在华山山腰主要以（NH₄）₂SO₄和NH₄NO₃的形式存在,而在华山山脚主要以NH₄HSO₄和NH₄NO₃的形式存在.华山山腰和山脚PM_2.5及其离子呈现出不同的日变化特征：山腰在12：00~16：00出现峰值,主要是因为边界层抬升和山谷风输送地表污染物的缘故;山脚则分别在白天08：00~12：00和夜晚00：00~04：00出现双峰值,这主要是由于早高峰交通排放增加和夜间大型载货卡车流量增大所致.利用阴阳离子当量平衡法及ISORROPIA Ⅱ模型进一步探讨了PM_2.5酸度特征,结果表明：华山山脚PM_2.5的酸度（pH=2.9±2.0）强于山腰（pH=3.2±2.3）.     

华北平原潮土酸度特征与酸化敏感性的初步探讨

采集华北平原潮土样品对其酸度特征和酸化敏感性进行了初步探讨.结果显示,过量施用氮肥导致的硝酸盐积累是华北平原潮土pH值下降的重要原因,硝酸根与土壤pH值呈显著负相关.碳酸钙溶解是当前潮土缓冲酸化的主要过程,决定着潮土对外界酸输入的响应方式和敏感程度.随着酸输入量的增加,低碳酸钙土壤的pH值迅速下降,但高碳酸钙的石灰性潮...     

沈阳市降水化学成分及来源分析

沈阳市2007年降水样品化学组分研究表明,该区降水pH值在4.89～8.02之间,雨量加权平均值为6.89,与杭州等南方地区相比,沈阳降水中离子浓度比较高,但降水的酸化程度和酸化频率却不高,表明沈阳市整体上降水没有呈现酸化,主要是碱性离子的中和作用.SO24-和Cl-是主要的阴离子,雨量加权平均值为330.00μeq·L-1和85.05μeq·L-1,分别占阴离子总量的60.32%和15.55%;Ca2+和NH4+是主要的阳离子,雨量加权平均值为291.17μeq·L-1和175.13μeq·L-1,分别占阳离子总量的49.51%和29.78%.季节变化特征研究表明离子浓度变化呈现秋冬高,春夏低的状态.NF计算结果表明NH4+和Ca2+具有较强的中和能力,而Mg2+和K+的中和能力比较小,相较于NH4+和Ca2+几乎可以忽略不计.利用富集系数法计算表明,SO24-和NO3-主要来源于人为输入,Cl-主要为海洋输入,NH4+和K+主要来源于土壤和人为活动的输入.     

黄山降水酸度及电导率特征分析

为了解黄山降水酸碱度和污染程度的总体特征,对2006～2011年黄山光明顶气象站常规监测的降水pH值和电导率进行了统计分析,结果表明:①该地区降水pH年均值在4.81～5.57,2009年之前,降水酸度加强,之后酸度减弱;降水平均pH值冬季最低(4.78),夏季最高(5.33);出现频率最高的降水事件为弱酸性到中性,总酸雨频率为46%,酸性降水累积雨量约占总雨量的45%.②年均降水电导率在16.91～27.84μS.cm-1,无明显年变化趋势.电导率在15μS.cm-1以下的降水发生频率最高,其次是15～25μS.cm-1之间.2010年2月～2011年12月,按日进行降水平行采样、存储、运送到实验室进行pH值与电导率测定和离子成分分析,对此期间的现场测定与实验室测定的两组pH值、电导率进行了比较分析.结果表明:①两组pH值间、两组电导率间都显著相关,但从山上现场到实验室,降水pH值向中性方向偏移,偏移幅度与降雨量和现场pH值有关,电导率的变化量与总离子浓度有关;现场pH值与电导率之间存在显著的负相关(r=-0.51).②使用一次性采样袋采样,pH值偏差变小,电导率之间相关性更强,两组pH与电导率间都存在明显的负相关.与中东部其他高山站的观测结果相比,黄山降水酸度弱,离子污染程度轻.     

DRAINAGE QUALITY AT DEEP COAL MINE SITES1

ABSTRACT: Samples were collected from the drainages of inactive deep coal mine sites located in eight states. Drainage quality was found to be highly variable, with a majority of sites exceeding federal effluent quality guidelines. Concentrations of trace metals including cadmium, mercury, zinc, and nickel were low. The presence of overburden calcareous material was shown to affect drainage quality. A consistent pattern of pH-acidity response was found to exist for the mine sites monitored. An empirical formula was developed to characterize this response.     

石灰中和法处理冶炼酸性生产废水的工艺优化

文章对冶炼厂酸性生产废水提出了常规石灰法处理和废水部分循环使用处理二种处理工艺,并指出常规石灰法处理工艺工艺过于复杂,处理成本较高,企业难以承受;而废水部分循环使用处理工艺可实现水的重复使用,节约水资源及处理费用,还可取得明显的环境经济效益。采用二级石灰中和沉淀法处理冶炼厂酸性生产废水可全面达标排放,采用两次分离有助于去除水中的Cu、Zn、Pb、Cd、As、F等有害物质,采用重力浓缩和压滤脱水方法对湿渣进行处理是一种最经济有效的方法。