气相色谱法测定土壤中丙酸、苹果酸、柠檬酸

用对甲苯磺酸对有机酸进行衍生化,没有太多的条件限制,方法简便,建立的分析方法应用于土壤中低分子量有机酸的测定,样品分析结果平均RSD在5%以内,平均回收率为97.1%~98.2%。本方法具有简单、高效灵敏、回收率高、重复性好等优点,可用于各种植物、食品、药材中低分子量有机酸的含量测定。     

超声提取-固相萃取小柱净化-气相色谱法测定土壤中14种有机氯农药

对土壤中14种有机氯农药的超声提取技术和磺化、固相萃取小柱两种净化方法进行系统研究。结果表明,超声提取节省提取时间,提高分析效率;磺化法和固相萃取小柱法都有净化作用,但磺化法使样品中的艾氏剂、狄氏剂和异狄氏剂全部损失;固相萃取小柱净化当丙酮-正己烷淋洗液体积比为1∶9、淋洗液收集8 mL时回收率>90%,干扰最小。方法检出限为0.63~2.59μg/kg,精密度(RSD,n=7)为1.17%~14.66%,基体加标平均回收率为82.78%~106.94%。方法用于生态地球化学调查评价批量土壤样品的实际分析,检测结果满足评价工作需要。     

气相色谱法测定地下水中拟除虫菊酯有机氯百菌清等24种农药残留

拟除虫菊酯类、有机氯、百菌清等农药均属于电负性强化合物,采用气相色谱-电子捕获检测器(GC-ECD)检测具有较高的灵敏度,但由于拟除虫菊酯类农药分子量较大,其灵敏度显著低于有机氯,使得各类化合物进行分类检测的流程长、分析效率低。本文通过优选分析色谱柱和进样口温度等条件,利用气相色谱的色谱柱程序升压功能实现了多类别24种农药残留的快速、准确测定。实验中以正己烷为溶剂进行液液萃取,Florisil固相萃取柱净化,选择有机氯专用色谱柱(RTX-CLPesticides 2)进行分析,GC-ECD仪器在0.5~6000 ng/mL浓度范围内呈线性,方法检出限为1.00~12.00 ng/L,低、中、高三个浓度水平的加标回收率分别为80.3%~116%、79.9%~117%、85.7%~102%,相应的精密度(RSD,n=7)为1.5%~6.8%、1.3%~7.6%、1.1%~6.8%。本方法选用的有机氯专用色谱柱(RTX-CLPesticides 2)对多组分、多类别目标化合物有更好的分辨率,较通用型色谱柱(DB-5MS)更具分析优势;采用的色谱柱程序升压技术解决了拟除虫菊酯类化合物在气相色谱柱中停留时间过长而导致的低灵敏度、峰拖尾等技术难题。此方法灵敏、经济,分析通量高,可有效地同时分析多种类农药残留物质。     

基于小麦籽粒降Cd率及土壤Cd形态变化评价蚯蚓对Cd污染土壤的修复效果

本研究基于小麦籽粒降Cd率、土壤中Cd生物可利用态(DTPA-Cd)含量和土壤Cd移除率评价蚯蚓(赤子爱胜蚯蚓)对两种Cd污染农田土壤(河南潮土及河北褐土)的修复效果。研究结果表明：两种土壤中,添加0.5%和1.0%(蚯蚓鲜重/土壤干重)蚯蚓均能够明显降低小麦对Cd的富集,改变Cd在小麦植物器官中的分布,显著降低小麦籽粒中Cd含量(P<0.05),籽粒降Cd率达到31.1%~43.5%,促使小麦籽粒生物量增加35.5%~62.7%。添加0.5%和1.0%蚯蚓可显著降低土壤中生物可利用态Cd(DTPA-Cd)含量(P<0.05),DTPA-Cd含量下降29.1%~40.8%,有利于促进土壤中生物可利用态Cd向生物不易利用的形态转化。0.5%和1.0%蚯蚓添加使土壤中Cd移除率达到6.05%~11.88%,明显高于对照组(P<0.05),说明蚯蚓具有很好的Cd污染农田土壤修复潜力。在低Cd污染农田土壤中,蚯蚓可以降低土壤中Cd含量,减少小麦对Cd的富集,同时降低小麦籽粒Cd含量,这一研究结果对于修复低Cd污染农田土壤、保证农产品安全和实现“边生产边修复”具有重要意义。     

高压密闭消解技术在土壤有效态样品前处理中的应用

土壤样品经有机酸浸提后,浸提出的溶液中存在大量有机酸及有机质,如未进行破坏处理,进入电感耦合等离子体发射光谱仪(ICP-OES)进样系统后容易堵塞雾化器、中心管、矩管等,或有颗粒黏附于中心管壁和矩管壁上,造成测定结果精密度和准确度差、空白高等问题,进而影响土壤有效态的综合评价。本文将土壤样品用有机酸(DTPA、草酸-草酸铵、柠檬酸等)浸提后,过滤或离心,吸取上清液加入高压密闭消解罐中,经电热板上处理,再加2mL浓硝酸,于180℃烘箱中保温至少3h,采用ICP-OES测定有效态元素铜锌铁锰镉铅镍铬钼硅的含量。本方法采用高压密闭消解技术处理土壤样品,各元素测定结果的相对标准偏差(RSD)为2.5%～5.9%,相对误差为-2.1%～5.2%,回收率为90.1%～103.2%,方法检出限为0.32μg/kg～0.038mg/kg;而采用以往高温炉中灼烧法、硝酸-高氯酸(硫酸)敞开消解法等技术手段,回收率为89.2%～100.5%,方法检出限为0.50μg/kg～0.050mg/kg,两者相比,本方法的测定结果稳定、空白低,分析周期短,适合批量样品的连续分析。     

超高效液相色谱-电喷雾串联质谱法同时测定土壤中四环素类抗生素及其降解产物

研究建立了超高效液相色谱电喷雾串联质谱法(UPLC/MS/MS)测定土壤中四环素(TC)、土霉素(OTC)、金霉素(CTC)、多西环素(DC)4种四环素类抗生素(TCs)及5种降解产物的残留分析方法。采用乙腈与EDTA-Mcllvaine缓冲液混合提取土壤样品中TCs,净化采用HLB固相萃取小柱,电离方式为ESI(+),定量方法为多反应监测(MRM)模式。在0.001~0.5 mg/kg范围内, 4种四环素类抗生素及其降解产物的峰面积与质量浓度的线性关系良好( R2>0.99)。仪器检出限为1.085~15.780 μg/kg,方法的定量限为3.617~42.526 μg/kg。在3个添加水平 0.05、0.1和 0.5 mg/kg下,除脱水四环素和差向脱水四环素(其回收率<30%)外,其余四环素类抗生素及代谢产物在土壤中的添加回收率为62.1%~87.6%,相对标准偏差为2.35%~13.42%。该方法线性关系良好,灵敏度高,适用于土壤中四环素类抗生素及其降解产物的残留分析。     

离子色谱法测定土壤中有效氟

利用离子交换-电导检测离子色谱法对土壤中有效氟进行测定。选用30 mmol/L氢氧化钾溶液作为淋洗液,流速1.20 mL/min,准确测定有效态(可提取态)氟含量。方法加标回收率为95%~108%,精密度好,检出限低,操作简单,对环境无污染,适合于土壤污染状况的调查。     

泡沫塑料吸附分离富集-电感耦合等离子体质谱法测定稀土矿石中的镓

采用电感耦合等离子体质谱法(ICP-MS)测定稀土矿石中的镓,高含量的稀土元素会造成严重的质谱干扰。本文采用聚氨酯泡沫塑料在6 mol/L盐酸介质中吸附样品溶液中的镓后,以0.5 mol/L氯化铵水浴加热解脱30 min,镓的吸附-解脱效率超过99%,稀土元素等干扰物质基本不进入解脱液中,即在富集镓的同时实现了镓与基体元素的高效分离,降低了质谱干扰。本方法检出限低(0.022μg/g),经土壤及水系沉积物标准物质验证,镓的测定值与标准值吻合(绝对偏差为0.38%~4.70%),实际稀土矿石样品的加标回收率为94.1%~100.6%,精密度(RSD)低于4%(n=12),可应用于分析一般地质样品以及稀土矿石中的镓。     

H+和有机酸对可变电荷土壤铝释放的动力学研究

利用流动搅动法研究了在模拟酸雨和低分子量有机酸条件下可变电荷土壤铝释放的动力学特征,结果表明,在pH3.5的模拟酸雨作用下,红壤和黄壤中流出液铝的浓度范围约为15～40μmol/L,铝的释放快反应来源于土壤交换性铝和有机络合态铝,铝的释放慢反应对应于含铝矿物的溶解。赤红壤和砖红壤上在0～300min内流出液铝的浓度范围约为1～5μmol/L,流出液pH值大于4.5,对H 的缓冲作用表现为阳离子交换、SO24-的专性吸附释放OH-和矿物表面的质子化;当流出液pH值小于4.5时,H 开始溶解土壤中的含铝固相,铝释放的最后浓度为20～30μmol/L。用相近pH值的有机酸溶出土壤铝的浓度比pH3.5的模拟酸雨要高,特别是在砖红壤上,开始就有大量铝的释放,其浓度为20～75μmol/L,红壤上是70～150μmol/L,随时间延长,流出液中的铝浓度分别为10～20μmol/L和20～30μmol/L。有机酸作用下铝的释放机制主要是有机酸被土壤吸附后,有机酸与位于表面晶格中的铝原子形成络合体,促进了铝的溶解;其次是有机酸的吸附掩盖了土壤表面的质子化过程,增强了酸的溶解,以及有机配体对铝的络合作用,增加了铝的释放量。不同有机酸对铝的溶出能力也有不同,其释放铝能力的大小为:柠檬酸>酒石酸>苹果酸,这取决于有机配体与铝的络合能力。     

吹扫捕集-气相色谱／质谱法测定土壤中挥发性有机化合物

建立了吹扫捕集-气相色谱/质谱技术测定土壤中挥发性有机化合物的方法,对标准模拟样品的基体选择、吹扫捕集条件、色谱条件等实验条件进行了考察。结果表明,方法检出限为0.20~0.60μg/kg,精密度(RSD,n=7)为2.78%~9.89%,基体加标平均回收率为81.5%~115.2%。方法准确可靠,用于批量样品的实际分析,检测结果良好。     

广东省普宁市土壤硒的分布特征及影响因素研究

开展了广东省普宁市区域土壤硒调查研究,采集了413个表层土壤样品(0～20 cm)和103个深层土壤样品(> 150 cm),测定了土壤全硒含量,据此研究土壤硒分布特征及其影响因素。结果表明,普宁市土壤全硒含量变化于0. 16～2. 01 mg/kg,平均值为0. 63 mg/kg,总体上处于中硒及高硒水平,不存在缺硒和硒过剩土壤。砂页岩风化形成的赤红壤全硒含量较高,平均值达0. 86 mg/kg,以侏罗系页岩母质发育的土壤全硒含量最高,平均值达0. 89 mg/kg;三角洲第四系沉积物发育形成的水稻土全硒含量最低,平均值为0. 41 mg/kg。回归分析表明,土壤全硒含量与铁铝含量、有机碳含量具有极显著正相关,与p H呈极显著负相关。影响普宁市土壤硒含量的主要因素是成土母质,土壤p H、有机碳和铁铝含量及土地利用方式对土壤全硒含量分布与富集也有一定的影响。     

福建省龙海市表层土壤硒含量及影响因素研究

在龙海市土壤地球化学调查数据基础上,开展土壤硒含量特征、影响因素分析等项研究工作,可为研究区富硒土地资源开发提供依据。本文通过采用原子荧光光谱法(AFS)对福建省龙海市表层土壤4394件样品硒全量进行了分析测试,结果表明:龙海市表层土壤的硒含量为0.031~2.361 mg/kg,平均值为0.354mg/kg,足硒、富硒土壤面积占全地区面积的88.69%。同时发现,成土母质、土地利用方式、土壤pH、有机质含量以及海拔高度是影响龙海市土壤硒含量的重要因素。火山凝灰岩区、花岗岩区成土母质发育的土壤硒含量较高;在不同土地利用方式中,林地土壤的硒含量最高,园地、耕地土壤的硒含量适中;土壤硒含量与有机质含量、海拔高度呈正相关,与pH呈负相关,说明在酸性、富含有机质的土壤环境中硒元素易于富集,尤其是高海拔的山地丘陵区土壤中硒的富集作用更加明显。本研究成果对龙海市土地的合理规划利用、富硒产业的科学发展具有重要价值。     

岩溶高原区农业地膜中邻苯二甲酸二乙基己酯的释放及其对覆膜土壤的影响

随着邻苯二甲酸酯类(PAEs)增塑剂在塑料大棚、地膜覆盖栽培技术中的广泛应用,我国农业土壤中已普遍存在邻苯二甲酸二乙基己酯(DEHP)污染问题。针对我国中西部岩溶高原区农业土壤中存在的DEHP环境问题,本文选取云南岩溶高原区的红壤及烟草地膜作为研究对象,通过田间试验模拟覆膜土壤环境,并采用气相色谱-质谱分析法检测农膜、土壤介质中DEHP含量,定量研究了地膜中DEHP的释放及其在覆膜土壤中的浓度分布特征。结果表明:覆盖于原状土壤上的地膜,其DEHP释放量最大,均值为13.57mg/kg;覆盖于加生物抑制剂土壤上的地膜,其DEHP释放量略高于未覆土壤地膜,前者DEHP平均值为10.83mg/kg,后者为10.77mg/kg;地膜中DEHP的释放表现为缓慢释放和集中陡升两个释放段,总体释放量随时间的延长而增加。两组覆膜土壤中DEHP的检出浓度范围分别为0.17～3.74mg/kg(原状土)、0.34～4.29mg/kg(加生物抑制剂土壤),在国内外覆膜农田土壤PAEs类化合物检出浓度范围内;土壤中DEHP含量具有随时间呈先增后减的变化规律。相关性分析表明土壤中DEHP主要来自于地膜中DEHP的释放。研究认为在短周期内岩溶高原红壤不会出现DEHP的累积,合理安排农作物的覆膜种植可有效削减土壤的有机污染。     

不同茶园茶叶氟含量及土壤氟的形态分布

通过对我国中西南产茶区12个茶园土壤样品和茶叶样品的采集,探讨了不同茶园茶叶氟含量和茶园土壤氟的形态分布规律。老叶和嫩叶氟含量分别为221～1 504 mg/kg和49.0～602 mg/kg,老叶氟含量是嫩叶的2.5～8.1倍。各形态氟含量随土壤层次加深没有统一变化规律,但各层土壤不同形态氟含量均为残渣态铁锰氧化物态＞有机结合态＞水溶态＞交换态。土壤pH值、有机质含量和阳离子交换量对茶园土壤氟的形态分布有不同程度的影响。老叶和嫩叶氟含量随水溶态氟含量的增加均呈显著增加趋势,但与其他形态氟含量没有显著的相关关系。     

Effect of amendment on phytoextraction of arsenic by Vetiveria Zizanioides from soil

The present study was undertaken to evaluate the growth response of Vetiveria zizanioides amended with organic amendments to arsenic (As) in contaminated soils and its ability to sequester As. The test results indicate that the plants exhibited high tolerance to As in the soils and their normal growth continued even though As concentration reached 500 mg/kg. However, when As concentrations in soils were in the range of 1000～2000 mg/kg the plants could not survive no matter whether the soils were amended. The accumulation of As in roots (185.4 mg/kg) was higher than that in shoots (100.6 mg/kg). The As level in the contaminated soil was reduced from 500 mg/kg to 214 mg/kg after six months of As phytoextraction. Microbial population was not affected in the As contaminated soil amended with dairy sludge, mycorrhizae and Azotobacter.     

岩溶区和碎屑岩区林地和农田土壤氮矿化过程对比研究

通过15N标记法和MCMC氮素转化模型,研究了岩溶区（石灰性土壤）和碎屑岩区（红壤）林地和农田土壤易分解有机氮矿化（M易）、难分解有机氮矿化（M难）和总有机氮矿化（M总）速率。结果发现,土壤矿化速率受土壤类型和土地利用方式的显著影响。林地石灰性土壤M总（3.71 mg N/kg）显著低于林地红壤（5.57 mg N/kg）,石灰性土壤MNlab（1.81 mg N/kg）与MNrec（1.90 mg N/kg）相近,而红壤M易（4.60 mg N/kg）显著高于M难（0.96 mg N/kg）。林地变为农田后,石灰性土壤M总 显著提高,而红壤显著降低。与林地相比,岩溶区农田土壤M易提高了72.5%,而M难下降了33.7%。碎屑岩区农田土壤M易和M难分别降低至2.47和0.46 mg N/kg。岩溶区土壤CaO和MgO含量与M易呈显著负相关,而与M难呈显著正相关,表明岩溶区土壤钙镁含量是影响氮矿化速率的重要因素。      

类芽孢杆菌对铜陵新桥矿区土壤中Cu化学形态的影响

采用Tessier五步连续提取法和红外光谱技术,研究类芽孢杆菌对铜陵新桥矿区重金属污染土壤中Cu化学形态的影响,初步探讨了Cu形态变化的机理。结果表明,不同投入量的类芽孢杆菌接种到土壤培养一周后,土壤溶液pH值降低,土壤中可交换态、有机结合态Cu含量增加,碳酸盐结合态、铁锰氧化物结合态和残渣态Cu的含量降低。土壤中可交换态、铁锰氧化物结合态和残渣态Cu含量的变化主要受土壤溶液的pH值控制;有机结合态升高主要与类芽孢杆菌菌数及其代谢产生的低分子量有机酸有关。类芽孢杆菌可以改变矿区土壤中Cu的化学形态,影响Cu的生物有效性。     

Total organic carbon in soils and its relation with manganese concentrations in soils and vegetation close to an abandoned manganese mine

This study aimed at quantifying the total organic carbon (TOC) present in soils within the proximity of the Kgwakgwe Mn oxide ore abandoned mine, Botswana, and establish its relationship with Mn concentrations in soils and vegetation based on multivariate and Geographical Information Systems (GIS) analytical techniques. Four hundred soil samples and 200 vegetation set samples were obtained from a 4 km² area close to the abandoned mine. The TOC in soil samples were determined using a carbon/hydrogen/moisture determinator, and Mn concentrations in soils and vegetation by atomic absorption spectrophotometry. Results were processed using the statistical package for social science (SPSS), GIS, and Remote Sensing (RS) techniques with the Integrated Land and Water Information System (ILWIS), Geosoft Oasis Montaj and ArcGIS software packages. The values for TOC in the soil samples from the study area ranged from 0 wt % to 7.91 wt %, with a mean of 1.90 wt %, and at the control area, from 4.07 wt % to 4.86 wt %. The range of concentrations of Mn in soils was from 36 mg/g to 24908 mg/g and for Mn concentrations in the vegetation samples from 26 mg/g to 3611 mg/g with a mean of 598 mg/g. Results of correlation coefficients depicted very weak negative association except Mn in soils/Mn in leaves which was weak but positive. The statistical data yielded four clusters as follows: cluster one consisted mainly of Mn in leaves, cluster two was constituted of Mn in soils, and cluster four had TOC. Cluster three was dominated by the three parameters but with negative t statistic. The spatial presentation of data presented revealed little or no vegetation in the south eastern area and those close to the mine workings, and some significant vegetation in the north western part of the study area. The low TOC in the soils is associated to low vegetation cover which is considered to have been influenced by the soil clay fraction mineralogy and high concentrations of Mn.     

Characteristics and distributions of humic acids in two soil profiles of the southwest China Karst area

Characteristics and distributions of humic acid (HA) and soil organic matter (SOM) in a yellow soil profile and a limestone soil profile of the southwest China Karst area were systematically investigated to reveal their evolutions in different soils of the study area. The results showed that characteristics and distribution of SOM along the two soil profiles were notably different. Total organic carbon (TOC) contents of soil samples decreased just slightly along the limestone soil profile but sharply along the yellow soil profile. TOCs of the limestone soils were significantly higher than those of the corresponding yellow soils, and C/N ratios of SOMs showed a similar variation trend to that of TOCs, indicating that SOM can be better conserved in the limestone soil than in the yellow soil. The soil humic acids were exhaustively extracted and further fractionated according to their apparent molecular weights using ultrafiltration techniques to explore underlying conservation mechanisms. The result showed that C/N ratios of HAs from different limestone soil layers were relatively stable and that large molecular HA fractions predominated the bulk HA of the top soil, indicating that HA in the limestone profile was protected while bio and chemical degradations were retarded. Combined with organic elements contents and mineral contents of two soils, we concluded that high calcium contents in limestone soils may play a key role in SOM conservation by forming complexation compounds with HAs or/and enclosing SOMs with hypergene CaCO₃ precipitation.     

Levels and sources of polycyclic aromatic hydrocarbons (PAHs) in selected irrigated urban agricultural soils in Accra, Ghana

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous organic pollutants in urban environments including urban soils. Elevated concentrations of PAHs in urban soils are caused by incomplete combustion of petroleum and coal. This study assesses 16 individual PAH compounds in a total of 112 surficial soil samples. The objective was to assess and compare the levels of contamination as well as examine the main sources of PAHs in four urban agricultural soils using molecular ratios of some specific hydrocarbons. The study showed that PAH levels in soil ranged from 1.23 ng/kg in soil collected from Dzorwulu to 2.95 ng/kg in soil collected from Ghana Broadcasting Cooperation (GBC) vegetable irrigation site. Of the total PAHs, the more water soluble PAHs (2–4 rings), which tend to be concentrated in the vapour phase were found to dominate the soils. The percentage dominance were Dzorwulu (52.8 %), Marine Drive (62.5 %), CSIR (53.2 %) and GBC (49.2 %). However, there were significant levels of the more carcinogenic PAHs (5–6 rings) present with percentages as 47.1, 37.5 46.8 and 50.8 % for Dzorwulu, Marine Drive, CSIR and GBC vegetable irrigation sites, respectively, and therefore, may impact negatively on public health. Based on the classification by the Institute of Soil Science and Plant Cultivation in Pulawy, Poland, urban soils in Accra could be classified as contaminated to different levels. Molecular ratios of Flu/pyr and PA/Ant were calculated to determine the main sources of PAHs. Results showed that PAHs could originate mainly from incomplete combustion of petroleum products, especially from atmospheric fallout from automobile exhausts. The study further showed that B(a)P concentration of 0.05 ng/kg in soil from GBC urban vegetable irrigation site requires immediate clean-up exercise and monitoring to mitigate human health impact.