Determination of Arsenic and Mercury in Livestock and Poultry Manure by HG-AFS

通过王水系统对畜禽粪便中砷、汞元素进行了提取,利用原子荧光光谱仪同时测定了畜禽粪便中的砷、汞,并对灯电流、负高压、载气流量等检测条件进行了优化.结果表明,用王水对畜禽粪便中的砷、汞前处理,可同时测定样品中的砷、汞.砷、汞检出限分别为0.051 5、0.009 6 μg· L-1.该法快速简便,回收率好,砷的回收率为91.9％～103.0％,汞的回收率为93.9％～101.5％.该法精密度高、结果准确,砷、汞的最大标准偏差分别为4.03％、4.47％,完全适用于畜禽粪便中砷、汞的检测.     

双通道原子荧光光谱法同时测定土壤中的砷和汞

对现有国标检测方法(GB/T 22105.1-2008和GB/T 22105.2-2008)进行改进,采用王水水浴浸提-双通道原子荧光光谱法同时测定土壤样品中砷、汞的含量。采用土壤国家一级标准物质GSS-3,GSS-8,GSS-9与山西农田土壤样品为试验对象,筛选得到检测砷、汞元素含量最佳实验条件及仪器工作条件。砷、汞的质量浓度分别在0~150μg/L,0~2μg/L范围内与荧光强度成良好的线性关系,线性相关系数均大于0.999,砷、汞的检出限分别为0.021,0.0015 mg/kg。测定结果的相对标准偏差为1.81%~4.64%(n=8),砷、汞的样品加标回收率分别为92.7%~103.0%,82.0%~95.5%。经国家一级标准物质验证,该法检出限、准确度和精密度均满足检测要求。改良后的方法可以同时准确、快速地测定土壤中砷、汞,极大地提高了工作效率,可以更好地适应当前大量的土壤分析工作。     

氢化物原子荧光光谱法测定虾中砷和汞

建立了氢化物原子荧光法同时测定虾中砷和汞的方法.研究了样品前处理及实验条件对测定砷、汞的原子荧光强度的影响,并探讨了共存离子对测定砷、汞的干扰和消除的方法.本方法具有操作简便、快速、灵敏度高等优点,砷和汞的检出限分别为0.026 μg/L和0.020 μg/L;相对标准偏差分别为1.7%～9.4%和1.2%～9.4%;回收率为98%～106%.     

微波消解-原子荧光光谱法测定皮革中砷和汞

建立了皮革中砷和汞的微波消解-原子荧光光谱测定方法。在优化的实验条件下,砷、汞含量分别在0.60～150ng/mL和0.10～20ng/mL范围内线性良好。砷、汞检出限分别为0.22ng/mL和0.04ng/mL。方法测定砷的回收率为96.0%～104%,汞的回收率为95.0%～110%。方法准确、灵敏、快速、可应用于皮革样品中砷和汞的同时测定。     

微波消解–原子荧光法同时测定PM2.5中砷、汞含量

采用微波消解–原子荧光法测定PM2.5中砷、汞含量。实验结果表明,当还原剂硼氢化钾的质量分数为2%、溶液介质酸度为4%(体积分数)盐酸时,同时测定砷、汞可获得最佳的荧光值。砷、汞测定的检出限分别为0.027,0.006μg/L,空白滤膜的加标回收率分别为95.3%~101.7%,96.0%~106.0%,样品的加标回收率分别为95.0%~103.5%,93.3%~110.0%。该法检出限低,准确度高,适用于环境空气PM2.5中砷、汞含量的测定。     

原子荧光光谱法快速测定出土文物体及周围土壤中砷与汞的研究

采用王水分解试样,原子荧光光谱法（AFS）测定了出土文物体及周围土壤中的砷、汞。结果表明,该测定的相对标准偏差分别为：0．8％～1．0％;1．4％～1．5％。方法回收率分别为：97．0％～102．0％;98．0％～104．0％。该法具有简便、快速、准确等优点,结果令人满意。     

王水消解-冷原子吸收光谱法测定土壤中汞

为了寻求一种更加适宜测定土壤中汞含量的测试方法,将检出限低、精密度高的冷原子吸收光谱法与便捷、高效的王水水浴消解土壤处理方式相结合,建立了王水消解-冷原子吸收光谱法测定土壤中汞。通过测定方法的线性相关性、方法检出限、准确度、精密度、加标回收率,并与原子荧光光谱法进行对比实验来评价该方法的有效性。王水消解-冷原子吸收光谱法在汞质量浓度0.0～1.0μg/L范围内线性良好,相关系数可以达到0.999 9,方法检出限为0.000 75mg/kg,土壤标准样品测试的相对标准偏差为4.0%～10.7%,实际样品加标回收率分别为93%～104%。采用原子荧光光谱法进行对比测试,原子荧光光谱法的方法检出限为0.002 5 mg/kg,相对标准偏差为4.8%～13.5%,加标回收率为104%～107%。结果表明,对于王水水浴消解土壤的方法不仅适用于原子荧光光谱法测定汞含量,同样可以应用于冷原子吸收光谱法中。所建立的王水消解-冷原子吸收光谱法具有更低的检出限,更优的准确度和精密度,有利于提高土壤样品测试的工作效率,值得推广。     

原子荧光光谱法快速测定粉煤灰中砷与汞

采用王水分解试样-原子荧光光谱法(AFS)测定粉煤灰中的砷、汞,方法回收率分别为98.5%~102.0%、85.0%~105.0%,相对偏差分别为1.9%~4.8%、0.6%~2.4%.方法具有快速、简便、灵敏等优点,对探讨粉煤灰在农业生态环境方面的综合利用颇有价值.     

端视ICP-AES法同时测定玩具涂料中可溶性铅、镉、汞、砷、铬、锑、硒和钡

采用端视电感耦合等离子体原子发射光谱(ICP-AES)法同时测定玩具涂料中可溶性铅、镉、汞、砷、铬、锑、硒和钡.对仪器的工作参数和被测元素的分析谱线进行了优化和选择.铅、镉、汞、砷、铬、锑、硒和钡的检出限分别为0.006、0.0009、0.012、0.023、0.000 8、0.013、0.030和0.0006 mg/L.定量下限分别为0.99、0.15、2.0、3.8、0.14、2.2、5.0和0.10 mg/kg.相对标准偏差为0.76%～2.72%(n=8),加标回收率为96.0%～104.0%.该法适用于玩具涂料中铅、镉、汞、砷、铬、锑、硒和钡的快速测定.     

氢化物发生-原子荧光光谱法同时测定食品添加剂碳酸钙中的砷和汞

应用氢化物发生-原子荧光光谱法同时测定食品添加剂碳酸钙中的砷和汞,并对样品中的主要成份及共存元素可能对检验结果的影响和实验条件进行了研究.结果表明,加入硫脲-抗坏血酸溶液后,碳酸钙中主要成份钙及可能存在的共存元素铁、铅、镉、铜、锑、硒、锡、铬、锌等不干扰砷和汞的测定.方法检出限为砷0.0124 μg/L,汞0.0009μg/L,回收率为砷101.8%～102.2%,汞102.5%～106.0%.精密度为砷0.37%,汞0.95%.建立的氢化物发生-原子荧光光谱法同时测定食品添加剂碳酸钙中砷和汞的分析方法能满足日常检验的要求.     

超高效液相色谱-串联质谱法检测鸡粪中16种残留抗生素

建立了固相萃取-超高效液相色谱-串联质谱(UPLC-MS/MS)同时检测畜禽粪便中四环素类、磺胺类、氟喹诺酮类和大环内酯类16种抗生素的分析方法.针对目标物化学性质和样品杂质情况,对质谱条件、提取液种类、超声功率等参数进行了优化.最终以50%乙腈(V/V)的磷酸盐缓冲溶液(pH=4)提取3次,经过超声、离心、旋蒸、稀释后,SAX-HLB串联小柱净化富集,用10 mL甲醇-丙酮混合液(80∶20,V/V)洗脱,35℃氮吹近干后,用含0.1%甲酸-甲醇(1∶1, V/V)定容,在UPLC-MS/MS多反应检测模式下进行定性及定量分析.结果表明,粪便中四环素类、磺胺类、氟喹诺酮类和大环内酯类抗生素的平均加标回收率为56.4%~94.6%,相对标准偏差(RSD)在2.6%~19.8%之间,方法检出限(LOD, S/N=3)和定量限(LOQ, S/N=10)分别为0.01~2.50 μg/ kg和0.05~7.90 μg/kg.本方法简便、稳定性好、灵敏度高、重现性好,适用于畜禽粪便中多种抗生素的同时检测.     

Quantification of multi-class antibiotics by UHPLC–MS/MS analysis combined with salt-assisted acetonitrile extraction: comparative evaluation of dairy and poultry manure

ABSTRACT

A comprehensive multiresidue method for the analysis of 33 antibiotics from 7 prevalent classes was comparably investigated for both dairy and poultry manure samples, which can be important pollution sources for the release of antibiotics into the environment. Following salting-out-assisted extraction with acetonitrile, the antibiotics were quantified with ultrahigh-performance liquid chromatography tandem mass spectrometry without a clean-up step. By changing the composition of the mobile phase for chromatography, a pronounced signal enhancement was achieved not only for tetracyclines (TCs) but also for other groups of antibiotics in the manure samples. Although the physicochemical properties of selected antibiotics were quite different, the apparent recovery values from dairy and poultry manure samples by using an extraction solvent comprising McIlvaine buffer and ethylenediaminetetraacetic solution at pH 3 were 86–121% and 89–113%, respectively. Apparent recovery of the antibiotics was not remarkably affected by the extraction solvent over a wide range of pH values, with the exception of the recovery of TC antibiotics from poultry manure, which was in the 53–55% range at pH 8. Furthermore, the poor performance of the analytical method for a few of the antibiotics in poultry manure was correlated with high metal and organic contents of the complicated matrix. The high suppression effects of co-eluted matrix components were compensated by constructing matrix-matched calibration curves and by using internal standards. Simultaneous quantification of seven different antibiotic classes with low limit of detection values varying from 0.38 to 31 μg kg^?1 for dairy manure and from 0.32 to 5.85 μg kg^?1 for poultry manure facilitated their monitoring. The application of the developed analytical method to dairy, broiler and layer-hen manure samples from confined animal feeding operations showed that a wide variety of antibiotics at high concentrations were found in broiler manure.     

微波消解-氢化物发生原子荧光光谱法同时测定化肥中砷、汞含量

采用微波消解样品前处理手段以及双道原子荧光光度计,建立了微波消解一氢化物发生原子荧光光谱法同时测定化肥中砷、汞含量的方法。通过试验确定了样品前处理方法,对负高压、灯电流,载气、屏蔽气、原子化器高度、酸度等测试条件进行了优化。在优化的工作条件下,砷、汞含量分别在0-50ng／mL和0—1．0ng／mL范围内与荧光强度呈良好的线性关系,线性相关系数分别为0．9996,0．9996,检出限分别为0．085,0．008ng／mL,回收率分别为88．8％～107．4％,90．0％～120％,测定结果的相对标准偏差均小于7％（n=6）。     

便携式气相色谱-质谱联用仪现场测定畜禽粪便堆肥中挥发性有机物

采用便携式气相色谱-质谱联用仪进行了畜禽粪便堆肥排放气体中挥发性有机物质的现场分析.结果表明,在堆肥排放气体中可检测到含硫物质、脂肪烃、芳香烃及含氯有机物共20种物质.在已定量的8种物质中,CS2浓度最高,达到204 mg/m3;CS2和二甲二硫超过《恶臭污染物排放标准》(GB1455-93)的限值;SO2和苯超过《室内空气质量标准》(GB/T 18883-2002)的限值.本方法避免了常规检测中易出现的组分分解等问题,SO2测定值较常规方法提高59.3％.本方法操作方便,结果准确,适于对挥发性有机化合物的在线监测.     

固相萃取-高效液相色谱法测定畜牧粪便中13种抗生素药物残留

建立了固相萃取-反相高效液相色谱法测定畜牧粪便中5种磺胺类、4种四环素类、2种喹诺酮类以及氯霉素和呋喃唑酮的检测方法.采用乙腈和0.01 mol/L草酸作为流动相分离4种四环素类和氯霉素,乙腈和0.025 mol/L醋酸铵作为流动相分离5种磺胺类和其它3种抗生素.结果表明,检测的13种抗生素出峰时间稳定,峰形较好,检出限0.01～0.05 mg/L,定量下限0.03～0.167 mg/L,采用柠檬酸缓冲液酸化的乙腈对猪粪便样品前处理,采用EDTA-McIlvaine提取液对鸡粪便样品前处理,两类样品均通过HLB固相萃取小柱纯化富集,回收率为54%～103%.该方法成功用于天津市4个畜牧养殖基地的20个畜牧粪便样品中抗生素的检测.结果表明,均有不同浓度的抗生素检出,浓度范围0.3～173 mg/kg.     

Determination of amprolium, carbadox, monensin, and tylosin in surface water by liquid chromatography/tandem mass spectrometry

Antibiotics present in the environment are recently considered as emerging contaminants, and have raised increasing concerns about their potential risks to ecosystems and human health. In addition to the utilization for treatment, antibiotics are also routinely added as supplements in livestock feed to promote animal growth. A portion of the administered dose used for these purposes can be excreted into animal manure, and land application of the animal manure as plant fertilizers enhances the dissemination of antibiotics in the environment. It is a common practice to simultaneously administer multiple classes of antibiotics to livestock in an animal production farm. This study attempts to develop a protocol to determine four commonly used veterinary pharmaceuticals, amprolium, carbadox, monensin, and tylosin, in surface runoff from a livestock farm. A single-cartridge solid-phase extraction procedure was developed to simultaneously extract these veterinary antibiotics from surface water which were subsequently analyzed by liquid chromatography/tandem mass spectrometry. The extraction recoveries of spiked samples ranged from 89 to 113%, and the limits of quantitation were 8, 25, 1, and 35 ng/L for amprolium, carbodox, monensin, and tylosin, respectively. In the surface runoff from a livestock farm, amprolium was most frequently detected with the concentration range of 10-288 ng/L. Monensin was frequently detected with concentrations up to 37 ng/L. Tylosin was detected in two out of eleven samples, and carbadox was not detected in the surface runoff. The results indicate that the developed analytical method can be utilized to determine multiple classes of veterinary antibiotics present in surface runoff originating from animal farms.     

Rapid determination of natural and synthetic hormones in biosolids and poultry manure by isotope dilution GC–MS/MS

The release of hormones into the environment due to land application of biosolids and manure is a cause of concern for their potential impacts. This paper presents the development of a rapid and sensitive method, based on extraction, for the analysis of 13 hormones in biosolids and poultry manure. A simultaneous derivatization of hydroxyl and ketone groups was carried out for the determination of hormones by GC–MS/MS. The method was validated in three matrices (sewage sludge, manure, and broiler litter). Recoveries from spiked samples at three concentration levels (50, 25, and 10 ng/g) ranged from 76 to 124% with relative SDs ≤ 16%. Method detection limits for the three matrices were in the range of 0.5–3.0 ng/g dry weight. The optimized method was applied to biosolid and poultry manure samples collected in Spain. Only seven of the 13 studied hormones were detected in the different samples. trans‐Androsterone was detected at high levels (up to 3.1 μg/g in biosolid samples). Estrone and estradiol were the two hormones detected at higher levels in layer manure, whereas estrone and 4‐androstene‐3,17‐dione presented the highest levels in broiler litter.     

Evaluation of Biogas Production Potential by Dry Anaerobic Digestion of Switchgrass–Animal Manure Mixtures

Anaerobic digestion is a biological method used to convert organic wastes into a stable product for land application with reduced environmental impacts. The biogas produced can be used as an alternative renewable energy source. Dry anaerobic digestion [>15% total solid (TS)] has an advantage over wet digestion (<10% TS) because it allows for the use of a smaller volume of reactor and because it reduces wastewater production. In addition, it produces a fertilizer that is easier to transport. Performance of anaerobic digestion of animal manure–switchgrass mixture was evaluated under dry (15% TS) and thermophilic conditions (55 °C). Three different mixtures of animal manure (swine, poultry, and dairy) and switchgrass were digested using batch-operated 1-L reactors. The swine manure test units showed 52.9% volatile solids (VS) removal during the 62-day trial, while dairy and poultry manure test units showed 9.3% and 20.2%, respectively. Over the 62 day digestion, the swine manure test units yielded the highest amount of methane 0.337 L CH₄ /g VS, while the dairy and poultry manure test units showed very poor methane yield 0.028 L CH₄/g VS and 0.002 L CH₄/g VS, respectively. Although dairy and poultry manure performed poorly, they may still have high potential as biomass for dry anaerobic digestion if appropriate designs are developed to prevent significant volatile fatty acid (VFA) accumulation and pH drop.     

微波消解-电感耦合等离体子质谱法(ICP-MS)同时测定畜禽粪便中7种重金属元素

粪便样品干燥、研磨后,称取0.25 g样品,加入8 mL硝酸,采用微波消解方法进行前处理。采用KED模式消除质谱干扰,采用内标校正消除非质谱干扰(Ge作为Cu、Zn、Cr的内标,Bi作为Hg和Pb的内标,Rh作为As和Cd的内标),建立了可同时测定畜禽粪便中Cu、Zn、Cr、As、Cd、Pb、Hg 7种重金属元素的微波消解-电感耦合等离子体质谱法。方法线性相关系数均在0.9995以上,检出限为0.005~0.305μg/L,加标回收率为83.6%~112%,相对标准偏差为0.70%~5.6%。方法灵敏度、准确度和精密度高,实用性强,适用于同时检测畜禽粪便中多种重金属元素,对畜禽粪便的科学还田具有指导意义。