有机氯农药和多氯联苯测定的样品净化方法

介绍了多氯联苯和有机氯农药环境样品的弗罗里硅土小柱、浓硫酸的分离、净化方法。经实际样品测定检验该方法，测定结果可靠。     

加速溶剂萃取-气相色谱质谱法同时测定土壤及沉积物中34种有机氯农药及18种多氯联苯类化合物

建立了加速溶剂萃取-气相色谱质谱法同时测定34种有机氯农药(OCPs)和18种多氯联苯类化合物(PCBs)的方法。当取样量为10. 0 g时,52种有机化合物的检出限为0. 03～0. 29μg/kg,以空白样品为基体进行加标回收试验,平均回收率为44. 7%～123. 0%,相对标准偏差(RSD,n=7)为1. 8%～21. 5%。该方法灵敏度高,实现了低浓度有机化合物的定量分析,分析结果准确可靠,满足土壤和沉积物中34种有机氯农药和18种多氯联苯类化合物分析的要求。     

全自动凝胶色谱净化-气相色谱法同时测定淡水鱼类中多氯联苯和有机氯农药等36种残留有机物

建立了淡水鱼类中多氯联苯和有机氯农药等36种半挥发性有机物的同时测定方法。样品用正己烷和丙酮(体积比为1∶ 1)进行提取,提取溶液经凝胶色谱和弗罗里硅土两级净化,浓缩后采用气相色谱法测定,回收率为70.3%~84.8%,检出限为0.05~0.20ng/g。该方法准确度和回收率较好,适合淡水鱼类中多氯联苯和有机氯农药含量的测定。     

快速溶剂提取-气相色谱法测定土壤中19种多氯联苯单体

采用快速溶剂提取-Florisil固相萃取柱净化-气相色谱法测定土壤中多氯联苯单体，探讨了有机氯农药对测定的干扰。方法在0ug／L-100ug／L范围内线性良好，19种多氯联苯单体的检出限为0．06ug／kg-0．36ug／kg，基体加标回收率为78．6％-120％，RSD为0．2％-5．1％。     

气相色谱-质谱法测定沉积物中的有机氯和多氯联苯

采用加速溶剂萃取法提取沉积物中的有机氯和多氯联苯,提取液用凝胶色谱法净化后用气相色谱-质谱法测定。方法在5.00μg/L~200μg/L范围内线性良好,当取样量为10.0 g时,方法检出限为0.03μg/kg~0.37μg/kg,空白样品2个质量比水平的加标回收率为70.8%~121%,测定结果的RSD为2.7%~11.5%。用该方法测定实际样品,结果 12个抽检的沉积物样品中多氯联苯均未检出,9个样品中有机氯检出。     

中空纤维膜萃取-气相色谱法测定水中有机氯农药

提出了中空纤维膜萃取-气相色谱法测定水中有机氯农药的方法。首先研究了8种有机氯农药的线性范围,然后测定了中空纤维膜萃取对水中有机氯农药的回收率,最后用中空纤维膜萃取-气相色谱法对实际水样进行检测。结果表明,8种有机氯农药在0.5~10μg/L范围内具有良好的线性关系,中空纤维膜萃取法对水中8种有机氯农药的富集倍数为389~464,回收率为77%~92%,可以满足分析要求。     

快速溶剂萃取-气相色谱-串联质谱法测定底泥中的有机氯农药

采用快速溶剂萃取、中性硅胶-中性氧化铝复合柱对底泥样品进行提取和净化,采用气相色谱-串联质谱法测定底泥中的30种有机氯农药。该方法的检测限为0.01~0.05 μg/kg,加标回收率为80.6%~110.5%,样品重复测定6次,均能得到较好的精密度,其相对标准偏差小于20%。结果证明,该方法灵敏度高、重复性好、准确度高、且快速简便,完全满足底泥中有机氯农药的测定要求。     

硅胶分离-气相色谱法测定海水样品中的有机氯农药及多氯联苯

建立了硅胶净化-具电子捕获检测器气相色谱(GC-ECD)测定海水样品中有机氯农药(OCPs)、多氯联苯(PCBs)的方法。海水样品经正己烷萃取,浓缩萃取液后过硅胶层析柱,通过梯度淋洗进行样品的净化和分离,采用GC-ECD进行分析测试。OCPs回收率达70.7%~109.2%,PCBs回收率达92.6%~119.2%。采用GC-MS进行辅助确证,结果表明,方法可行。     

加速溶剂萃取和净化-气相色谱-串联质谱法测定典型污染场地土壤中多氯联苯残留

建立了加速溶剂萃取同步净化-气相色谱-三重四极杆串联质谱法测定污染场地土壤中7种指示性多氯联苯的方法。对加速溶剂萃取、净化、色谱柱、串联质谱离子对、碰撞电压等条件进行了优化。萃取和净化过程合二为一,串联质谱法提高了7种多氯联苯的灵敏度。7种多氯联苯在0.1～100μg/L质量浓度范围内线性良好,线性相关系数为0.999 80～0.999 99,方法检出限为0.004～0.010μg/kg,回收率为84.8%～97.3%,相对标准偏差为2.4%～8.5%。运用网格法采集了华东某典型污染场地土壤中31个土壤样品,分析了该场地7种指示性多氯联苯的残留特征。7种多氯联苯的检出率为100%,检出范围为0.096～3 661μg/kg,各点平均值为307μg/kg。各采样点中多氯联苯的残留程度存在很大差异,局部点位受到了较重污染,与封存点相近的部分点位残留较外围位置高。土壤中多氯联苯同系物以三氯联苯、四氯联苯、五氯联苯为主,占同系物总量的98.2%。该污染场地土壤多氯联苯主要是低氯代联苯污染,土壤中多氯联苯的毒性效应评估处于中等水平,污染以点源污染为主,且已有较大程度扩散。     

微波萃取-气相色谱法测定土壤中有机氯残留

采用微波萃取-硅镁吸附剂净化-气相色谱法测定土壤中有机氯农药，优化了试验条件。方法线性良好，8种有机氯农药的检出限为0.09ng／g-0.62ng／g，样品测定的RSD为2.6％-13.2％，基质加标平均回收率为93.7％-112％，质控样的测定结果与参考值相吻合。     

Accessing indoor fungal contamination using conventional and molecular methods in Portuguese poultries

Epidemiological studies showed increased prevalence of respiratory symptoms and adverse changes in pulmonary function parameters in poultry workers, corroborating the increased exposure to risk factors, such as fungal load and their metabolites. This study aimed to determine the occupational exposure threat due to fungal contamination caused by the toxigenic isolates belonging to the complex of the species of Aspergillus flavus and also isolates from Aspergillus fumigatus species complex. The study was carried out in seven Portuguese poultries, using cultural and molecular methodologies. For conventional/cultural methods, air, surfaces, and litter samples were collected by impaction method using the Millipore Air Sampler. For the molecular analysis, air samples were collected by impinger method using the Coriolis μ air sampler. After DNA extraction, samples were analyzed by real-time PCR using specific primers and probes for toxigenic strains of the Aspergillus flavus complex and for detection of isolates from Aspergillus fumigatus complex. Through conventional methods, and among the Aspergillus genus, different prevalences were detected regarding the presence of Aspergillus flavus and Aspergillus fumigatus species complexes, namely: 74.5 versus 1.0 % in the air samples, 24.0 versus 16.0 % in the surfaces, 0 versus 32.6 % in new litter, and 9.9 versus 15.9 % in used litter. Through molecular biology, we were able to detect the presence of aflatoxigenic strains in pavilions in which Aspergillus flavus did not grow in culture. Aspergillus fumigatus was only found in one indoor air sample by conventional methods. Using molecular methodologies, however, Aspergillus fumigatus complex was detected in seven indoor samples from three different poultry units. The characterization of fungal contamination caused by Aspergillus flavus and Aspergillus fumigatus raises the concern of occupational threat not only due to the detected fungal load but also because of the toxigenic potential of these species.     

Strong correlations between metal in mollusk soft tissue and nonresistant sediment fraction: a tool for biomonitoring intertidal zone of the Persian Gulf,Iran

Cadmium (Cd) and lead (Pb) were determined in three species of mollusks and associated sediment. Samples were collected from two locations along the intertidal zone of the Persian Gulf near Bandar Abbas. The study was conducted during the spring of 2011, 10 sediment samples and 15 mollusks from each of the following species: Saccostrea cucullata, Solen brevis, and Callista umbonella, were simultaneously collected. Soft tissue, shell, and sediment were tested for metals using an atomic absorption spectrophotometer. Geochemical fractions of the sediment were examined for metals using a sequential extraction technique. Our results indicate that over half of Cd and Pb in the sediment had natural origins. Independent sample t test showed statistically significant (p?<?0.05) inter-tissue differences in accumulation of Cd and Pb. Soft tissue of C. umbonella contained highest levels of Cd. Pb accumulation was highest in S. brevis shell. Significant correlations (p?<?0.05) were found between Cd in the soft tissue of C. umbonella and its levels in the geochemical fractions of the sediment. Lead levels in the resistant geochemical fractions of the sediment and S. brevis shell were significantly correlated. Our results suggest that soft tissue of C. umbonella and shell of S. brevis are reliable biomonitoring tools for Cd and Pb, respectively.     

Voltammetric trace determination of mercury using plant refuse modified carbon paste electrodes

Citrus limon peel (kitchen waste) and Leucaena leucocephala seeds (agricultural waste) were used as a modifier for fabrication of modified carbon paste electrode for determination of mercury in aqueous sample using differential pulse anodic stripping voltammetry. Mercury was adsorbed on electrode surface at open circuit and anodic stripping voltammetric scan was run from ?0.5 to 0.5 V. Various electrochemical parameters including amount of modifier, supporting electrolyte, accumulating solvent, pH of the accumulating solvent, and accumulation time were investigated. The effect of presence of other metal ions and surfactants was also studied. In comparison C. limon peel proved to be a better modifier than L. leucocephala seed biomass. This was justified by electrode characterization using cyclic voltammetry that indicated decrease in resistance of electrode when C. limon peel was used as modifier and increase when modifier was L. leucocephala seeds. Maximum current response was obtained using 5 % C. limon peel biomass, hydrochloric acid as supporting electrolyte, acetate buffer of pH 6 as an accumulating solvent, 10-min accumulation time, and scan rate of 50 mV/s. Linear calibration curves were obtained in the concentration range 100 to 1,000 μg L^?1 of mercury for accumulation time of 10 min with limit of detection of 57.75 μg L^?1 and limit of quantification of 192.48 μg L^?1. This technique does not use mercury as electrode material and, therefore, has a positive environmental benefit.     

Biosorption properties of Cd(II), Pb(II), and Cu(II) of extracellular polymeric substances (EPS) extracted from Aspergillus fumigatus and determined by polarographic method

Extracellular polymeric substances (EPS) were extracted from Aspergillus fumigatus using cationic exchange resin technique. The EPS were mainly composed of polysaccharide and low quantities of protein and nucleic acid. Biosorption of Cd(II), Pb(II), and Cu(II) of EPS was investigated as a function of pH using differential pulse polarography and the Ruzic model. Results showed that the EPS biosorption capacity determined using either the direct titration curves i?=?f(C _M) or the method proposed by Ruzic (Analytica Chimica Acta 140:99–113, 1982) were coincident. Cu(II) had the highest affinity with EPS followed by Pb(II) and Cd(II). The total number of binding sites for Cu(II) and Cd(II) increased with pH in the range of 4.0–7.0. Similar trend was observed for Pb(II) at pH?4.0–5.0, while precipitates were observed at pH?6.0 and 7.0. The conditional binding constants of these three metals displayed low levels of fluctuation with pH and ranged from 4.02?±?0.02 to 5.54?±?0.05.     

Evaluation of optimal conditions for determination of low selenium content in shellfish samples collected at Todos os Santos Bay,Bahia, Brazil using HG-AFS

This work proposes a procedure for the determination of total selenium content in shellfish after digestion of samples in block using cold finger system and detection using atomic fluorescent spectrometry coupled hydride generation (HG AFS). The optimal conditions for HG such as effect and volume of prereduction KBr 10 % (m/v) (1.0 and 2.0 ml) and concentration of hydrochloric acid (3.0 and 6.0 mol L^?1) were evaluated. The best results were obtained using 3 mL of HCl (6 mol L^?1) and 1 mL of KBr 10 % (m/v), followed by 30 min of prereduction for the volume of 1 mL of the digested sample. The precision and accuracy were assessed by the analysis of the Certified Reference Material NIST 1566b. Under the optimized conditions, the detection and quantification limits were 6.06 and 21.21 μg kg^?1, respectively. The developed method was applied to samples of shellfish (oysters, clams, and mussels) collected at Todos os Santos Bay, Bahia, Brazil. Selenium concentrations ranged from 0.23?±?0.02 to 3.70?±?0.27 mg kg^?1 for Mytella guyanensis and Anomalocardia brasiliana, respectively. The developed method proved to be accurate, precise, cheap, fast, and could be used for monitoring Se in shellfish samples.     

Research on the relationship between the fractional coverage of the submerged plant Vallisneria spiralis and observed spectral parameters

The present paper discusses the relationship between the coverage fraction of submerged plants and the observed spectral characteristics. The purpose of this paper is to validate a remote sensing technology to monitor the change in the plant composition of a water body. In the current study, the reflectance spectra of the submerged plant Vallisneria spiralis at different fraction coverages of the wetland in Hangzhou Bay were measured. The relationships between the fraction coverage of V. spiralis and simulated Quickbird normalized difference vegetation index (NDVI), red edge, and other spectral characteristic parameters were established. The results showed that the spectral reflectance characteristics of submerged plant V. spiralis were mainly in the visible light (490–650 nm) and near infrared (700–900 nm). The rate of change of the blue band curve and simulated Quickbird NDVI showed a higher correlation with the V. spiralis coverage, so estimation models of the fraction coverage were constructed using these parameters. The estimated fraction coverage of V. spiralis with different models were validated with ground data, and the accuracy of estimation models was assessed. The most suitable estimated fraction coverage of V. spiralis was obtained using the rate of change of the blue band curve and simulated Quickbird NDVI. The present work demonstrated a method to monitor the distribution and dynamical variation of submerged plants at the large scale.     

An assessment of the optimal scale for monitoring of MODIS and FIA NPP across the eastern USA

Robust monitoring of carbon sequestration by forests requires the use of multiple data sources analyzed at a common scale. To that end, model-based Moderate Resolution Imaging Spectroradiometer (MODIS) and field-based Forest Inventory and Analysis (FIA) data of net primary productivity (NPP) were compared at increasing levels of spatial aggregation across the eastern USA. A total of 52,167 FIA plots and colocated MODIS forest cover NPP pixels were analyzed using a hexagonal tiling system. A protocol was developed to assess the optimal scale as an optimal size of landscape patches at which to map spatially explicit estimates of MODIS and FIA NPP. The optimal mapping resolution (hereafter referred to as optimal scale) is determined using spatially scaled z-statistics as the tradeoff between increased spatial agreement as measured by Pearson’s correlation coefficient and decreased details of coverage as measured by the number of hexagons. Spatial sensitivity was also assessed using land cover assessment and forest homogeneity using spatially scaled z-statistics. Pearson correlations indicate that MODIS and FIA NPP are most highly correlated when using large hexagons, while z-statistics indicate an optimal scale at an intermediate hexagon size of 390 km². This optimal scale had more spatial detail than was obtained for larger hexagons and greater spatial agreement than was obtained for smaller hexagons. The z-statistics for land cover assessment and forest homogeneity also indicated an optimal scale of 390 km².     

Estimation of nested spatial patterns and seasonal variation in the longitudinal distribution of Sicyopterus japonicus in the Datuan Stream, Taiwan by using geostatistical methods

This study attempts to determine the scale-dependent hierarchical spatial variation and longitudinal distributions of Sicyopterus japonicus year round. The distribution of S. japonicus in the Datuan Stream in northern Taiwan was surveyed during the fall and winter 2007, as well as the spring and summer of 2008. The spatial structure of S. japonicus density was modeled using geostatistics. The longitudinal distributions of S. japonicus density were then estimated using kriging and hydrology distance with nested variogram models. Variography results indicate that nested variogram models could reflect the hierarchical structure in the spatial variation of seasonal S. japonicus density, with the small, median, and large ranges representing three nested scales. Models for the four seasons were consistent in that they shared the same shape of variogram models with various ranges and sill values. This model shape consistency implies stationary spatial correlations in the longitudinal fish distribution across the four seasons. The Kriging geostatistical method based on the multiple scales nested variogram models also provided robust estimates of S. japonicus densities at unsampled sections. We conclude that S. japonicus densities exhibit hierarchical patterns and variation in the four seasons along the study stream. Geostatistical methods with a nested variograms and hydrological distance are a highly effective means of delineating the hierarchical structure in longitudinal patterns of S. japonicus density in each season, providing estimates of the S. japonicus density for hierarchically structured spatial distributions and expanding knowledge of S. japonicus beyond the limits imposed by spatial and temporal scales.     

Degradation of polyethylene by Trichoderma harzianum—SEM,FTIR, and NMR analyses

Trichoderma harzianum was isolated from local dumpsites of Shivamogga District for use in the biodegradation of polyethylene. Soil sample of that dumpsite was used for isolation of T. harzianum. Degradation was carried out using autoclaved, UV-treated, and surface-sterilized polyethylene. Degradation was monitored by observing weight loss and changes in physical structure by scanning electron microscopy, Fourier transform infrared spectroscopy, and nuclear magnetic resonance spectroscopy. T. harzianum was able to degrade treated polyethylene (40 %) more efficiently than autoclaved (23 %) and surface-sterilized polyethylene (13 %). Enzymes responsible for polyethylene degradation were screened from T. harzianum and were identified as laccase and manganese peroxidase. These enzymes were produced in large amount, and their activity was calculated using spectrophotometric method and crude extraction of enzymes was carried out. Molecular weight of laccase was determined as 88 kDa and that of manganese peroxidase was 55 kDa. The capacity of crude enzymes to degrade polyethylene was also determined. By observing these results, we can conclude that this organism may act as solution for the problem caused by polyethylene in nature.