水中苯胺类化合物分析的难点

结合实验研究了水中苯胺类化合物的测定难点和影响因素，包括样品保存和水样中悬浮物的影响。苯胺类化合物易被氧化，样品不易保存且受悬浮物的影响。研究结果表明：样品中未加入抗氧化剂进行保存时，部分苯胺类化合物迅速降解；当样品中加入80 mg/L硫代硫酸钠进行保存时，部分苯胺类化合物的保存时间可以延迟2~3 d后降解。样品中悬浮物对联苯胺萃取影响较大，回收率偏低，可以通过调节样品pH至酸性后过滤，再将滤液调至中性后进行萃取，回收率明显提高。笔者同时讨论了消除与补偿基质干扰的方法，包括色谱分离条件和检测器条件的选择、优化，内标法、空白基质匹配标准校正法和工作曲线法等定量方法的选择。     

统计学在垃圾焚烧飞灰浸提液重金属检测准确性研究中的应用

为提高复杂基体重金属检测准确性,在使用电感耦合等离子体发射光谱法检测生活垃圾焚烧飞灰浸提液时,进行标准曲线法、标准加入法和内标法3种定量校准方法比对。3种方法报出结果经过加标回收率换算后的样品原值具有明显一致性,使用统计学方差齐性和单因素方差分析验证了该一致性成立,表明内标法的精密度和准确度与标准曲线法、标准加入法无显著性差别。以3种方法样品原值的算数平均值作为样品最佳估计值评价各方法实际报出结果准确性,标准加入法准确性最好;稀释后的样品内标法加标回收率明显优于标准规定,受稀释倍数影响不大,工作效率高,满足HJ 781—2016质控要求,建议可作为该标准的补充;建议批量样品检测时优先采用内标法。3种方法样品原值一致性的验证,有助于执法、科研中对于复杂基体重金属物质含量的准确判断。     

ASE-GC-MS法测定土壤中酞酸酯类有机物质量控制指标探索

用ASE(加速溶剂萃取)-GC-MS法测定土壤中酞酸酯类有机物,得到平行样品157组数据、重复性实验12组数据、全程序空白55组数据、空白加标122组数据、基体加标80组数据的质量控制指标的范围值,酞酸酯类有机物的检出限为8~26μg/kg。     

吹扫捕集-气相色谱-质谱法测定企业土壤及修复场地中的苯胺

建立了吹扫捕集-气相色谱-质谱法测定土壤中苯胺浓度的分析方法,优化了前处理条件,并对色谱柱进行优选。采用该方法对企业污染场地土壤中的苯胺进行测定,结果显示,苯胺在20~4000μg/kg范围内线性关系良好,最低检出限为1.5μg/kg,相关系数(r)为0.9991,加标回收率为90.1%~97.6%,相对标准偏差(RSD)为5.4%~7.9%。该方法解决了苯胺分析过程中峰形拖尾的问题,测试效率高、检出限低、精密度和准确度好,适用于企业土壤及修复场地中的苯胺测定。     

土壤介质中酞酸酯类污染物分析方法研究

介绍了加压流体提取(PFL、ASE)提取-GPC净化-GC/MS分析土壤中酞酸酯类污染物方法的程序和质控要求,研究了每个步骤对分析六种目标物准确度和精密度的影响以及测定实际土壤样品的情况.结果显示,加压流体提取(PFL)、浓缩和GPC净化各步骤全程序空白加标回收率分别在86.3%～108%、78.5%～117%和87.4%～103%范围,精密度均在15%以内.在实际土壤样品中加入六种酞酸酯标准的加标回收率在45.2%～103.4%范围内,其相对标准偏差8%～23%.     

原子荧光法测定土壤中砷的质量控制评价标准研究

组织多家实验室开展监测,研究了原子荧光法测定土壤中砷的质量控制措施及其评价标准。研究表明,RSD、RD、RSD'、RD'、RE和加标回收率是土壤监测的重要质量控制措施,对于标准样品,其评价标准分别为RSD≤10%、RD≤30%、RSD'≤20%、RD'≤30%、RE≤±20%、空白加标回收率为95%~105%、标准样品加标回收率为75%~110%;其与两个土壤标准样品系列、与土壤中砷的浓度均没有显著的相关性。     

酸化吹气-气相分子法测定固体废物中硫化物

采用酸化吹气装置结合气相分子吸收光谱仪对固体废物中硫化物进行测定。考察酸性试剂的选取、加入量及酸化吹气反应时间对测定结果的影响,得出最佳的前处理条件为加入10 mL体积比为1∶1的磷酸,酸化吹气45 min。为确保吸收液中硫化物不被氧化,向吸收液中加入一定量抗氧化剂。结果表明:当抗氧化剂加入量为5 mL时,吸收液中硫化物的浓度可在6 h内保持稳定。方法的标准曲线相关系数为0.999 9,检出限为0.19 mg/kg,实际固体废物样品的相对标准偏差为2.7%～6.1%,加标回收率为91.0%～93.0%。将气相分子吸收光谱法和亚甲基蓝分光光度法进行比对,结果表明2种方法对固体废物中硫化物的测定无显著差异。     

城市污水中PCBs的分析及其QA/QC研究

报道了一种城市污水中痕量PCBs的分析方法,并进行了QA/QC研究,采用二氯甲烷萃取剂对城市污水进行液-液萃取,联合运用浓硫酸和硅胶层析柱将PCBs与杂质分离,以毛细管GC-ECD和内标法对PCBs定量.空白加标回收试验得出,PCBs的回收率为58%～125%,标准偏差为0.00173～0.00778μg/L,相对标准偏差为1.58%～12.43%.以实际城市污水作为加标基质,得出加入污水中的19种PCBs的分析方法回收率为57.6%～129.2%,方法的检测限为0.010～0.056μg/L,满足了US EPA对PCBs回收率要求.经过3次平行测定,测得实际城市污水中PCBs含有9种PCBs,PCBs总量的平均值为0.0235μg/L,相对标准偏差为9.63%,该分析方法所需的仪器简便、容易操作.     

微波消解-石墨炉原子吸收法测定土壤中铊

通过研究土壤消解体系、混合基体改进剂的使用、石墨管类型的选择和标准加入定量过程对测定结果的影响,建立了适用于土壤中重金属铊的微波消解-平台石墨炉原子吸收方法。结果表明,使用HNO_3-HF-H_2O_2消解体系对土壤进行微波消解,石墨炉原子吸收测定过程采用Pd(NO_3)_2/Mg(NO_3)_2混合基体改进剂和平台石墨管,土壤中铊的检出限可达0.05 mg/kg,线性相关系数为0.996,加标回收率在95.0%~105.0%。使用该方法测得的结果与ICP-MS法比较,无统计学差异。改进后的方法具有简单快捷、灵敏度高、重现性好、线性范围广、结果准确等优势,易于推广使用。     

微库仑法测定新疆棉浆粕企业废水中可吸附有机卤素AOX

建立微库仑滴定法测定水质中可吸附有机卤素AOX的方法,考察3种活性炭柱对于空白的影响。实验结果表明,AOX的检出限为2.19μg/L,相对标准偏差为2.80%,纯水中高、中、低加标回收率在92.5%~107%,新疆棉浆粕企业废水中加标回收率为96.0%~101%。实验室空白也只有新购开封的耶拿原装活性炭小柱能满足标准要求的空白值(<30μg/L)。     

RELATIONSHIP BETWEEN BASAL SOIL RESPIRATION RATE, TREE STAND AND SOIL CHARACTERISTICS IN BOREAL FORESTS

Soil respiration is considered to represent the overall microbial activity reflecting mineralisation of organic matter in soil. It is the most commonly used biological variable in soil studies. In long-term monitoring of forested areas, there is a need for reference values for soil microbiological variables in different forest ecosystems. In this study we describe the relationship between soil respiration rate, tree stand and humus chemical characteristics of boreal coniferous forests stands. Soil respiration rate was higher in pine dominated than in spruce dominated study sites when the result was calculated on dry matter bases. However, when calculated on area bases, the result was opposite and no difference was found when the soil respiration rate was calculated on organic carbon bases. Irrespective of the main tree species, the soil respiration rate was equal in different development classes but not equal in soil fertility classes, i.e. within forest site types based on differences in ground vegetation. Respiration rates were clearly higher in mesic sites when calculated on dry matter, C_org or area bases. However, soil respiration rate did not correlate with soil chemical variables indicating site fertility. Soil respiration rate on dry matter basis was at a lower level in the south and on more fertile sites, and on the other hand at a higher level in older stands and on sites with a thicker organic layer.     

Influence of solvent and soil type on the pressurised fluid extraction of PAHs

Pressurised fluid extraction (PFE) of polycyclic aromatic hydrocarbons (PAHs) from a certified reference material (CRM) 524 has been firstly optimised following a central composite design. The instrumental parameters of the PFE (pressure, temperature, extraction time and number of solvent cycles) were studied in order to obtain maximum extraction yields. Neither pressure nor extraction time or temperature seemed to have any significant effect on the extraction yield, therefore one extraction cycle was enough to exhaustively extract all the PAHs from CRM 524. Once the instrumental conditions were established, the extraction yields obtained with eight different solvents or solvent mixtures [acetone, dichloromethane, acetonitrile, acetone-dichloromethane (1 + 1 v/v), acetone-isohexane (1 + 1 v/v), isohexane, methanol and toluene] from the CRM 524 were compared and showed that the best recoveries were obtained with acetone-isohexane (1 + 1 v/v). Finally, the effect of sand, silt, clay and the organic matter content of soil was investigated with respect to recovery of PAHs by PFE with different solvents or solvent mixtures for aged soil samples. In this case, eight soils with different sand, silt, clay and organic matter contents were slurry spiked with PAHs and aged for 19 days. Three aliquots of each slurry spiked soil were extracted with the previously mentioned solvents and the results were studied by means of principal component analysis (PCA) of the whole data set (soil composition, solubility parameter of the solvent and recoveries of all PAHs) and partial least squares (PLS). Clay and organic matter content and the squared solubility parameter have the highest correlation with the recovery of PAHs from soil samples.     

Soil adsorption studies of a rice herbicide,cyhalofop-butyl,in two texturally different soils of India

The ability of herbicides to be adsorbed by the soil and sediment and their tendency to be desorbed are some of the most important factors affecting soil and water contamination. Therefore, a sorption study was conducted to evaluate the adsorption of cyhalofop-butyl, butyl (2R)-2-[4-(4-cyano-2-fluorophenoxy) phenoxy] propanoate, in the sandy clay loam and clayey soils using a batch equilibrium method. The adsorption of cyhalofop-butyl was found positively related with the clay and organic carbon content. Freundlich constants (K _f) of cyhalofop-butyl in the clayey and sandy clay loam were found to be 13.39 and 2.21, respectively. Sorption coefficients (K _oc) and distribution coefficients (K _d) were found to be 265.38 and 2,092.79, and 1.38 and 11.48, for sandy clay loam and clayey soils, respectively. The adsorption isotherm suggested a relatively higher affinity of cyhalofop-butyl to the adsorption sites at low equilibrium concentrations. The low value of the soil organic carbon partition coefficient (K _oc) of cyhalofop-butyl in the sandy loam soil suggested its weaker adsorption in soil and thus increased its risk of mobility into water sources; hence, it should be used judiciously to prevent groundwater contamination     

Distribution and fractionation of cadmium, copper, lead, nickel, and zinc in a calcareous sandy soil receiving municipal solid waste

This study was conducted to evaluate the degree of mobility and fractionation of cadmium (Cd), copper (Cu), lead (Pb), nickel (Ni), and zinc (Zn) after the addition of municipal solid sewage sludge (MSS) in a sandy calcareous soil. Treatments were (1) soil application of MSS, (2) soil application of enriched municipal solid waste compost (EMSS), and (3) control soil. The MSS application represented a dose of 200 Mg dry weight per hectare. Soil columns were incubated at room temperature for 15 days and irrigated daily with deionized water to make a total of 505 mm. At the end of leaching experiments, soil samples from each column were divided into 14 layers, each being 1 cm down to 10 and 2.5 cm below that and analyzed for diethylenetriaminepentaacetic acid (DTPA)-extractable Cd, Cu, Pb, Ni, and Zn. The fractionation of the heavy metals in the top five layers of the surface soil samples was investigated by the sequential extraction method. All soil layers of the columns receiving MSS and EMSS had significantly higher concentrations of DTPA-extractable heavy metals than control soil. The maximum concentration of heavy metals in treated soil was in the surface layer and declined significantly with depth. Sequential extraction results showed that in the treated soil, a major proportion of Cd, Pb, and Ni was associated with organic matter (OM) and exchangeable (EXCH) fractions, and a major proportion of Cu and Zn was associated with residual (RES) and OM fractions. Based on relative percent, Pb, Cd, and Ni in the EXCH fraction was higher than Cu and Zn in soil leached with MSS and EMSS, suggesting that application of this MSS to a sandy calcareous soil, at the loading rate used here, may pose a risk in terms of groundwater contamination with Pb, Cd, and Ni.     

吹扫捕集气相色谱质谱法测定土壤中挥发性有机物

建立了吹扫捕集气相色谱质谱法同时测定土壤中卤代烃类、苯系物类、氯代苯类等二十多种挥发性有机物.使用模拟土壤和实际土壤样品优化了吹扫时间、吹扫温度等参数;采用内标法绘制了校正曲线,各目标化合物5个浓度水平的响应因子的相对标准偏差均小于20%,相关系数均大于0.999;测定了方法检出限,采用2g土壤,各目标化合物方法检出限界于0.02～1.00μg/kg;对两种总有机碳含量的实际土壤样品进行了加标回收实验,回收率范围64%～123%.     

Changes in labile soil organic matter fractions following land use change from monocropping to poplar-based agroforestry systems in a semiarid region of Northeast China

Labile fractions of soil organic matter (SOM) respond rapidly to land management practices and can be used as a sensitive indicator of changes in SOM. However, there is little information about the effect of agroforestry practices on labile SOM fractions in semiarid regions of China. In order to test the effects of land use change from monocropping to agroforestry systems on labile SOM fractions, we investigated soil microbial biomass C (MBC) and N, particulate organic matter C (POMC) and N (POMN), as well as total organic C (TOC) and total N (TN) in the 0- to 15-cm and the 15- to 30-cm layers in 4-year-old poplar-based agroforestry systems and adjoining monocropping systems with two different soil textures (sandy loam and sandy clay loam) in a semiarid region of Northeast China. Our results showed that poplar-based agroforestry practices affected soil MBC, POMC, and POMN, albeit there was no significant difference in TOC and TN. Agroforestry practices increased MBC, POMC, and POMN in sandy clay loam soils. However, in sandy loam soils, agroforestry practices only increased MBC and even decreased POMC and POMN at the 0- to 15-cm layer. Our results suggest that labile SOM fractions respond sensitively to poplar-based agroforestry practices and can provide early information about the changes in SOM in semiarid regions of Northeast China and highlight that the effects of agroforestry practices on labile SOM fractions vary with soil texture.     

Effect of vegetation change from native broadleaf forest to coniferous plantation on selected soil properties

The objective of this study was to examine the effects of vegetation change from a native broadleaf forest to a coniferous plantation on selected soil properties, including soil texture, pH, organic matter, total nitrogen (N), total phosphorus (P), exchangeable cations (Ca²⁺, K⁺, Na⁺), and cation exchange capacity (CEC). Results showed that the amount of clay particles, Ca²⁺, and K⁺ values significantly increased, whereas Na⁺, total N, and organic matter and soil pH values decreased on the treatment plot after vegetation change. Soil acidity also increased and soil textural group changed from moderately fine-textured soils (clay loam) to medium-textured soils (loam) under both control and treatment plots. Organic matter, total N, and Na⁺ values increased, whereas Ca²⁺ concentration decreased through time on the control plot. Soil pH, total P, K⁺, and CEC did not show significant changes through time on the control plot.     

Factors affecting metribuzin retention in Algerian soils and assessment of the risks of contamination

Metribuzin is a widely used herbicide around the world but it could lead to soil and water contamination. Metribuzin retention on a silty–clay agricultural soil of Algeria was studied in laboratory batch experiments to assess the contamination risk of the groundwater. Factors conditioning the fate of metribuzin were investigated: soil nature, metribuzin formulation, NPK fertilizer, and soil pH. Freundlich sorption isotherms gave the coefficients K _F between 1.2 and 4.9 and 1/n _a between 0.52 and 0.93. The adsorption is directly dependent on organic and clay soil contents. Formulated metribuzin (Metriphar) reduces the adsorption (K _F?=?1.25) compared to pure metribuzin (K _F?=?2.81). The addition of an NPK fertilizer decreases the soil pH (6.67 for the soil without fertilizer and 5.86 for 2 % of fertilizer) and increases metribuzin adsorption (K _F is 4.83 for 2 % of fertilizer). The pH effect on the adsorption is corroborated in experiments changing the soil pH between 5 (K _F is 4.17) and 8 (K _F is 1.57) under controlled conditions. Desorption isotherms show a hysteresis and only 30 to 40 % of the initially adsorbed metribuzin is released. The estimated GUS index is ≥2.8 for a DT50?≥?30 days. K _F values and the hysteresis show that metribuzin is little but strongly retained on the soil. Formulated metribuzin and addition of fertilizer affect the retention. However, the GUS index indicates a high mobility and a significant risk of leaching. The most appropriate risk management measure would be an important increase in organic matter content of the soil by addition of organic amendments.     

溶解性有机碳对微库仑法测定水中可吸附有机卤素的影响

微库仑法测水样中可吸附有机卤素(AOX)受多种因素影响,其中溶解性有机碳(DOC)的影响非常显著。DOC对微库仑法2种前处理方法(双柱法和振荡法)的影响差异很大。双柱法受DOC影响较小,当DOC浓度小于1 000 mg/L时,AOX加标回收率范围为94.0%~104%。振荡法受DOC影响较明显,随着DOC浓度的升高,AOX回收率持续下降,当DOC浓度达到1 000 mg/L时,AOX加标回收率下降至72.1%,但DOC浓度小于100 mg/L时,AOX加标回收满足方法要求。进一步研究发现,DOC对振荡法的影响主要由于竞争吸附降低了活性炭对AOX的吸附容量,而非吸附速率,虽然增大活性炭用量可在一定程度上减小DOC对AOX测定的影响,但对样品进行稀释是减少DOC影响的最简单高效的办法。同时,DOC对不同类型的有机卤代物影响不同,有机溴受DOC影响程度小于有机氯。