Determination of organophosphorus pesticides by gas chromatography with mass spectrometry using a large‐volume injection technique after magnetic extraction

A fast and efficient method was developed for the extraction and determination of organophosphorus pesticides in water samples. Organophosphorus pesticides were extracted by solid‐phase extraction using magnetic multi‐walled carbon nanotubes and determined by gas chromatography with ion‐trap mass spectrometry. Parameters affecting the extraction were investigated. Under optimum conditions of the method, 10 mg magnetic multi‐walled carbon nanotubes were added into 10 mL sample. After 2 min, adsorbent particles settled at the bottom of test tube with a magnet. After removing aqueous supernatant, the analytes were desorbed with acetonitrile. Then, 70 μL of acetonitrile phase was injected into the gas chromatography and mass spectrometry system that had an ion‐trap analyzer. To achieve high sensitivity, the large‐volume‐injection technique was used with a programmed temperature vaporization inlet, and the ion‐trap mass spectrometer was operated in single ion storage mode. Under the best conditions, the enrichment factors and extraction recoveries were in the range of 113–124 and 74–103%, respectively. The limits of detection were between 3 and 15 ng/L, and the relative standard deviations were < 10%. This method was successfully used for the determination of organophosphorus pesticides in dam water, lagoon water, and river water samples with good reproducibility and recovery.     

Simultaneous determination of three organophosphorus pesticides in different food commodities by gas chromatography with mass spectrometry

A sensitive and selective gas chromatography with mass spectrometry method was developed for the simultaneous determination of three organophosphorus pesticides, namely, chlorpyrifos, malathion, and diazinon in three different food commodities (milk, apples, and drinking water) employing solid‐phase extraction for sample pretreatment. Pesticide extraction from different sample matrices was carried out on Chromabond C₁₈ cartridges using 3.0 mL of methanol and 3.0 mL of a mixture of dichloromethane/acetonitrile (1:1 v/v) as the eluting solvent. Analysis was carried out by gas chromatography coupled with mass spectrometry using selected‐ion monitoring mode. Good linear relationships were obtained in the range of 0.1–50 μg/L for chlorpyrifos, and 0.05–50 μg/L for both malathion and diazinon pesticides. Good repeatability and recoveries were obtained in the range of 78.54–86.73% for three pesticides under the optimized experimental conditions. The limit of detection ranged from 0.02 to 0.03 μg/L, and the limit of quantification ranged from 0.05 to 0.1 μg/L for all three pesticides. Finally, the developed method was successfully applied for the determination of three targeted pesticides in milk, apples, and drinking water samples each in triplicate. No pesticide was found in apple and milk samples, but chlorpyrifos was found in one drinking water sample below the quantification level.     

Fast and Selective Determination of Pesticides in Water by Automated On-Line Solid Phase Extraction Liquid Chromatography Tandem Mass Spectrometry

An automated on line-solid phase extraction (SPE) liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed for the determination of 17 polar pesticides in water. Minimizing sample pretreatment and using a fast chromatographic separation, the method allowed a sample to be processed in 15 minutes. The MS analysis was performed by Data Dependent Acquisition, using the triggered Multiple Reaction Mode function that provided analyte confirmation, thus enhancing selectivity without compromising sensitivity. In fact, the optimized method enabled the determination of the considered pesticides at the ultratrace level, with detection limits in the range 0.07–1.65 ng/L (propazine and atrazine-desisopropyl, respectively); the only exception was linuron that showed a slightly higher detection limit (12.2 ng/L). The optimized method was then applied to real water samples; five pesticides were determined in river water, in the range 1.17–14.2 ng/L, while four were measured in drinking water, in the range 0.91–2.25 ng/L.     

固相萃取-气相色谱-质谱联用同时测定河水和海水中87种农药

采用固相萃取-气相色谱-质谱联用技术,建立了河水和海水中87种农药(24种有机磷、15种有机氯、12种唑类、9种拟除虫菊酯类、5种氨基甲酸酯类、7种酰胺类及15种其他新型农药)的多残留同时分析方法。优化了影响分离效果和灵敏度的仪器参数,考察了固相萃取柱柱型及水样体积、pH、盐度的影响,采用NH2柱优化了净化效果,内标法和替代物法用于数据的质量控制。结果表明: 在最佳条件下,各目标农药的方法检出限为0.1～6.6 ng/L;以实际河水和海水为基底,在5 ng/L和20 ng/L的加标水平下,绝大多数目标农药的回收率为60%～120%,相对标准偏差(n=4)为0.01%～9.7%。该法灵敏、准确,已成功地应用于福建九龙江河口区表层水样中多种类农药的复合污染监测,检出包括5种有机磷类、3种酰胺类、4种唑类、3种氨基甲酸酯类、2种拟除虫菊酯类等农药20种。     

Alkanol-based supramolecular solvent microextraction of organophosphorus pesticides and their determination using high-performance liquid chromatography

A sensitive method for extraction and determination of three organophosphorus pesticides (chlorpyrifos, diazinon, phosalone) using a supramolecular solvent (SUPRAS) made of inverted hexagonal aggregates of alkanol and high-performance liquid chromatography with ultraviolet detection (HPLC–UV) was developed. The studied factors were alkanol amount, THF percentage (v/v), pH and vortex time. According to the full factorial design results, the effective parameters were alkanol amount, THF percentage (v/v) and pH. Then, a CCF was applied to obtain optimal conditions. The optimized conditions were obtained at 100 mg of alkanol, 5% of THF and pH 3.9. The limits of detection of pesticides were 0.5–1.3 ng/mL. The linearity was 1.6–500.0 ng/mL for different pesticides. Relative standard deviations for intra- and inter-day extraction of pesticides were 3.3–5.0 and 5.1–6.3, respectively, for five measurements. The method was also successfully applied for the determination of the pesticides in fruit juice and tap water samples.     

Selective solid-phase extraction using molecularly imprinted polymer for the analysis of polar organophosphorus pesticides in water and soil samples

An analytical methodology for the analysis of four polar organophophorus pesticides (monocrotophos, mevinphos, phosphamidon, omethoate) in water and soil samples incorporating a molecularly imprinted solid-phase extraction (MISPE) process using a monocrotophos-imprinted polymer was developed. Binding study demonstrated that the polymer showed excellent affinity and high selectivity to monocrotophos. The MISPE procedure including the clean-up step to remove any interferences was optimized. The accuracy and selectivity of the MISPE process developed were verified using a non-imprinted (blank) polymer and a classical ENVI-18 cartridge as the SPE matrix during control experiments. The use of MISPE improved the accuracy and precision of the GC method and lowered the limit of detection. The recoveries of four polar organophosphorus pesticides (OPPs) extracted from 1 L of river water at a 100 ng/L spike level were in the range of 77.5-99.1%. The recoveries of organophosphorus pesticides extracted from a 5-g soil sample at the 100 microg/kg level were in the range of 79.3-93.5%. The limit of detection varied from 10 to 32 ng/L in water and from 12 to 34 microg/kg in soil samples. The molecularly imprinted polymer (MIP) enabled the selective extraction of four organophosphorus pesticides successfully from water and soil samples, demonstrating the potential of molecularly imprinted solid-phase extraction for rapid, selective, and cost-effective sample pretreatment.     

Simultaneous extraction and determination of various pesticides in environmental waters

A simple and rapid method was developed for the simultaneous analysis of nine different pesticides in water samples by gas chromatography with mass spectrometry. A number of parameters that may affect the recovery of pesticides, such as the type of solid‐phase extraction cartridge, eluting solvent in single or combination and their volumes, and water pH value were investigated. It showed that three solid‐phase extraction cartridges (Strata‐X, Oasis HLB, and ENVI‐18) produced the greatest recovery while ethyl acetate/dichloromethane/acetone (45:10:45, 12 mL) followed by dichloromethane (6 mL) was efficient in eluting target pesticides from solid‐phase extraction cartridges. Different water pH values (4–9) did not show a significant effect on the pesticides recovery. The optimized method was verified by performing spiking experiments with a series of concentrations (0.002–10 μg/L) in waters, with good linearity, recovery, and reproducibility for most compounds. The limit of detection and limit of quantification of this optimized method were 0.01–2.01 and 0.02–6.71 ng/L, respectively, much lower than the European Union environmental quality standard for the pesticides (0.1 μg/L) in waters. The proposed method was further validated by participation in an interlaboratory trial. It was then subsequently applied to river waters from north‐east Scotland, UK, for the determination of the target pesticides.     

Magnetic core micelles as a nanosorbent for the efficient removal and recovery of three organophosphorus pesticides from fruit juice and environmental water samples

Sodium dodecyl sulfate coated amino‐functionalized magnetic iron oxide nanoparticles were used as an efficient adsorbent for rapid removal and preconcentration of three important organophosphorus pesticides, chlorpyrifos, diazinon and phosalone, by ultrasound‐assisted dispersive magnetic solid‐phase microextraction. Fabrication of amino‐functionalized magnetic nanoparticles was certified by characteristic analyses, including Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, and transmission electron microscopy. Affecting parameters on the removal efficiency were investigated and optimized through half‐fractional factorial design and Doehlert design, respectively. The analysis of analytes was performed by high‐performance liquid chromatography with ultraviolet detection. Under the optimum conditions, extraction recoveries for 20 ng/mL of organophosphorus pesticides were in the range of 84–97% with preconcentration factors in the range of 134–155. Replicating the experiment in above condition for five times gave the relative standard deviations <6%. The calibration curves showed high linearity in the range of 0.2–700 ng/mL and the limits of detection were in the range of 0.08–0.13 ng/mL. The proposed method was successfully applied for both removal and trace determination of these three organophosphorus pesticides in environmental water and fruit juice samples.     

固相萃取-GC/MS法测定水样中20种有机氯农药

建立了用固相萃取小柱提取和净化、GC/MS定性定量同时测定水样中20种有机氯农药的方法。方法采用OasisHLB固相萃取小柱萃取富集水样,二氯甲烷洗脱,加入菲-d₁₀作为内标,利用GC/MS进行定性定量,步骤简便,线性响应良好,干扰小,方法检出限为0.21～0.72 ng/L（按水样1L计）,加标回收率为64.8%～122%,RSD为1.2%～11.0 %。成功利用该方法对广西实际河水样品进行了检测。结果表明方法可以同时满足环境水样中20种痕量有机氯农药的测定。     

高效液相色谱-串联质谱法测定烟草中有机磷农药的残留量

建立了一种基于液相色谱-串联质谱法(LC-MS/MS)定量分析微量有机磷农药残留的方法,并应用于烟草中农药残留物的定量检测。采用乙腈超声提取烟草中的有机磷农药残留,以甲醇-水（含0.1%乙酸铵）(体积比为95∶5)为流动相,经高效液相色谱分离,以串联质谱在多反应监测(MRM)模式下测定,在2.5 min内完成了甲胺磷、乙酰甲胺磷、乐果、敌百虫、毒死蜱5种常用有机磷农药的定量分析。5种农药在1~200 μg/L内的线性关系良好(r>0.998),平均回收率为77%~104%,检出限为1.0~5.0 μg/kg。     

基于磁性共轭微孔聚合物的超高效液相色谱-串联质谱法测定果蔬中7种有机磷杀虫剂

建立了基于磁性共轭微孔聚合物的磁固相萃取-超高效液相色谱-串联质谱（UPLC-MS/MS）测定果蔬中7种有机磷杀虫剂的方法。将亚苯基亚乙炔基修饰的Fe₃O₄与1,3,5-三溴苯、1,3,5-三乙炔苯反应,制备磁性共轭微孔聚合物,材料能有效吸附共轭结构的有机磷杀虫剂,并在外磁场中实现便捷磁分离。方法的检出限（LOD）为0.12~5.0 ng/kg,加标回收率为80.8%~125%,相对标准偏差（RSD）小于6%（n=5）。方法应用于分析市场上果蔬样品中7种有机磷杀虫剂,检出含量为1.1~500.0 ng/kg。该方法灵敏度高,准确可靠,对果蔬中有机磷杀虫剂的检测具有良好的应用潜力。     

Determination of multiclass pesticides in river sediments via matrix solid-phase dispersion extraction and gas chromatography–tandem mass spectrometry

A fast and environment-friendly analytical method was implemented to determine multiclass pesticides in river sediments. Twenty-three pesticides—organochlorine pesticides, organophosphorus pesticides, and triazines—were extracted via matrix solid-phase dispersion (MSPD) and analyzed by gas chromatography–tandem mass spectrometry (GC–MS/MS). Florisil demonstrated excellent analytes uptake capability as the extractant phase, with suitable selectivity for treating complex sediment samples. Under defined extraction conditions, the MSPD–GC–MS/MS method demonstrated robustness in the n inter-day analysis of sediments from different sources, providing limit of quantifications (LOQs) between 5 and 15 ng/g, linear responses in the range between LOQs and 150 ng/g, extraction recoveries of 71%–106%, and precision, assessed as relative standard deviation below 20%. The MSPD significantly reduced samples and solvents’ consumption, providing critical environmental gains compared to traditional extraction methods like Soxhlet. Finally, the method was applied to analyze sediment samples from three different collection areas of the Subachoque River (Cundinamarca, Colombia), demonstrating a fast, efficient, confident, and profitable analytical tool for pollution control and monitoring in environmental samples. The method allowed us to determine the current use in Colombia of banned pesticides under the 2001 Stockholm Convention.     

在线固相萃取-超高效液相色谱-三重四极杆质谱法测定水源水和饮用水中107种典型农药及代谢产物

为进行我国水体中农药风险监测,针对水体中农药种类多、浓度低的特点,建立了在线固相萃取-超高效液相色谱-串联质谱法快速筛查和检测水源水及饮用水中107种典型农药及代谢产物(有机磷类、有机氮类、有机杂环类、氨基甲酸酯类、酰胺类、苯甲酰脲类、新烟碱类等)的方法。样品经0.22 μm孔径亲水性聚四氟乙烯滤膜过滤后,通过自动进样器取5 mL样品注入在线固相萃取系统,经X Bridge C₁₈在线固相萃取柱吸附后用纯水淋洗,以乙腈和0.1%甲酸水溶液为流动相对在线固相萃取柱梯度洗脱后再经ACQUITY HSS T₃色谱柱分离,采用电喷雾离子源正离子及负离子模式分析检测,外标法定量。以水源水及饮用水作为基质,对其准确度和精密度进行方法学验证,结果表明:107种农药及代谢产物在不同范围内线性关系良好(r²>0.995),方法检出限(LOD, S/N=3)为0.03~1.5 ng/L,定量限(LOQ, S/N=10)为0.1~5.0 ng/L。将目标分析物在1、20、50 ng/L水平下加标,水源水和饮用水中的加标回收率分别为60.6%~119.8%和61.2%~119.0%,相对标准偏差(RSD, n=6)分别为0.3%~18.6%和0.4%~17.1%。用该方法测定水源水和饮用水中的农药残留,结果显示,酰胺类、三嗪类除草剂、三唑类杀菌剂与烟碱类、氨基甲酸酯类杀虫剂有较高的检出率,其中水源水中检出含量为0.1~97.1 ng/L,饮用水中检出含量为0.1~93.6 ng/L。该方法适用于水源水和饮用水中107种典型农药及代谢产物的痕量分析测定,有效提高了水体中农药类物质的检测效率,实际应用价值较高。     

Development and validation of an HPLC-DAD method for the simultaneous determination of most common rice pesticides in paddy water systems

Rice crop is mainly cultivated in large river basins which constitute unique ecosystems and their ecological quality is invaluable. However, the high loads of pesticides used in rice cultivation contribute to the contamination of the water resources in such rice-cultivated regions. To regularly monitor the quality of such water resources there is a need for a rapid and sensitive multi-residue analytical method. This study presents the development and validation of a new analytical method for the simultaneous determination of most rice pesticides including penoxsulam, tricyclazole, propanil and its main metabolite 3,4-dichloroaniline, azoxystrobin, molinate, profoxydim and deltamethrin. A solid-phase extraction (SPE) procedure followed by high performance liquid chromatography (HPLC) with diode array detection (DAD) was used. A C₁₈ RP column operated at 30°C was utilised and the analytes were separated with a mobile phase of acetonitrile/water mixture in a linear gradient. Clean-up of water samples and isolation of pesticides was performed on SPE Bakerbond octadecyl cartridges and an ethyl acetate-dichlomethane mixture (9?:?1 v/v, 2?mL) was used for elution. Method validation was performed by means of intra-day (n?=?5) and inter-day accuracy and precision (n?=?8), sensitivity and linearity. The relative recoveries of the pesticides in paddy water samples were acceptable (80.6–110.2%) and the relative standard deviation (RSD%) ranged from 1.9 to 7.6%. Limits of detection (LOD) and limits of quantification (LOQ) varied from 0.1 to 0.8?ng?mL^?1 and 0.25 to 2.0?ng?mL^?1 respectively, depending on the analyte. The method was subsequently applied for the determination of pesticide residues in paddy and canal water samples. Tricyclazole was the most frequently detected pesticide at the highest concentrations, while herbicides were less frequently detected and at lower concentrations. The method described could be a valuable tool for regular monitoring of surface water systems in rice-cultivated basins.     

Continuous solid-phase extraction and gas chromatographic determination of organophosphorus pesticides in natural and drinking waters

A simple, rapid continuous-flow solid-phase extraction method with gas chromatographic detection for the determination of organophosphorus pesticides is proposed. The continuous system consists of an adsorbent column where pesticides are preconcentrated and subsequently eluted with ethyl acetate. Various sorbent materials were assayed of which RP-C18 was found to provide the best results, with a sorption efficiency close to 100%. A comparative study of the determination of pesticides in aqueous samples was conducted using gas chromatography with nitrogen-phosphorus (NPD) and flame ionization (FID) detection. The detection limits of the method for 10 ml of sample were between 50-130 ng/l and 4.5-1 1.7 microg/l with NPD and FID detection, respectively. The method was used to determine organophosphorus pesticides in river, pond, well and tap waters, all with good precision (2.9-4.3%) and recoveries ranging from 93.8 to 104.5%.     

亚临界水萃取及气相色谱-串联质谱法检测红茶中多种农药残留

建立了亚临界水萃取及气相色谱-串联质谱(GC-MS/MS)检测红茶中21种有机氯和拟除虫菊酯农药残留的方法。在萃取压力为5 MPa条件下,样品经150 ℃的亚临界水提取15 min后,将目标物转移至丙酮-正己烷(1:1, v/v)中,经ENVI-Carb固相萃取净化小柱净化,DB-5毛细管气相色谱柱分离,在多反应监测(MRM)模式下进行MS/MS检测,基质匹配溶液内标法定量。各目标物在5.0～320.0 μg/L范围内线性关系良好,相关系数均大于0.99,其定量限(信噪比(S/N)＞10)为50 ng/g,检出限(S/N＞3)为10 ng/g。茶叶基质中添加50、100和200 ng/g的标准品时,21种农药的回收率为70.18%～119.98%,相对标准偏差(RSD)为5.01%～11.76%。该方法的灵敏度、准确度和精密度均符合农药残留测定的技术要求,适用于红茶中有机氯和拟除虫菊酯农药残留的检测。     

Ultra-pressure liquid chromatography-electrospray tandem mass spectrometry for multiresidue determination of pesticides in water

A multiresidue analysis method has been developed for the determination of pesticides in water by ultra-performance liquid chromatography (UPLC) combined with tandem mass spectrometry (MS/MS). The selected pesticides represent a broad range of polarity and volatility [benzoylcyclohexanedione (mesotrione and sulcotrione); chloroacetamide (acetochlor, alachlor, dimethenamide, and metolachlor); phenoxyacetic acid (2,4-D and MCPA); phenoxypropionic (dichloprop and mecoprop); phenylurea (chlortoluron, diuron, isoproturon, linuron, and metoxuron); sulfonylurea (foramsulfuron, iodosulfuron, and nicolsulfuron); triazine (atrazine, cyanazine, desethylatrazine (DEA), desisopropylatrazine (DIA), simazine, and terbutylazine)]. The analytes were extracted using solid-phase extraction (SPE). The separation was carried out on an acquity UPLC BEH C18 column (1.7 microm, 50 mm x 1 mm ID) using a gradient elution profile and mobile phase consisting of 0.1% formic acid in water and acetonitrile. The pesticides were detected with a tandem mass spectrometer after being ionised positively or negatively (depending on the molecule) using an electrospray ionisation (ESI) source. To achieve the suitable extraction conditions for sample preparation, several parameters affecting the efficiency of SPE such as the nature of the sorbent and the eluent, extractant volume and pH were studied. The best recovery was obtained by the extraction with an Oasis HLB cartridge and 3 mL of a solution of acetonitrile/dichloromethane (1:1, v/v) at pH 2. The average recoveries of the pesticides in different samples ranged from 82 to 109%. The weight least squares (WLS) linear regression was used to calculate the limits of detection and quantification (LOD and LOQ) because the dispersion was heteroskedastic. All the pesticides could be correctly quantified at a concentration level of 50 ng L(-1) and most of them could be detected at a concentration inferior or equal to 8 ng L(-1). Efficiency and robustness of this method were evaluated by the analysis of several samples of real natural water.     

Determination of aromatic amines in environmental water samples using solid-phase extraction modified with sodium dodecyl sulphate and micellar liquid chromatography

Extraction and determination of seven aromatic amines in environmental water samples were performed with solid-phase extraction (SPE) and micellar liquid chromatography (MLC) using experimental design. Extraction of aromatic amines was carried out with a C₁₈ cartridge modified with sodium dodecyl sulphate (SDS). The washing solution and elution solvent for extraction of aromatic amines were aqueous solution containing 5% (v/v) acetonitrile and 5% (v/v) acetone and 3 mL methanol, respectively. The chemometrics approach was applied for the separation optimisation of these compounds using MLC. Different mobile phase compositions were used for modelling based on retention times to obtain the best separation using central composite design. The optimum mobile phase composition for separation and determination of analytes in water samples was 69 mM SDS, 9% v/v 1-propanol and pH = 6.4. Recoveries were between 84.8–93.5% with relative standard deviation (RSD) less than 5.8% (n = 5). Limits of detection and linear range were 1–4.5 and 3.1–125.0 µg/L, respectively. The proposed method was applied to determine the aromatic amines in real samples (river and well waters). Amount of 4-nitroaniline and 3-nitroaniline in river water sample were 2.15 and 1.91 µg/L, respectively.     

Ultrapreconcentration and determination of organophosphorus pesticides in water by solid‐phase extraction combined with dispersive liquid–liquid microextraction and high‐performance liquid chromatography

Solid‐phase extraction coupled with dispersive liquid–liquid microextraction was developed as an ultra‐preconcentration method for the determination of four organophosphorus pesticides (isocarbophos, parathion‐methyl, triazophos and fenitrothion) in water samples. The analytes considered in this study were rapidly extracted and concentrated from large volumes of aqueous solutions (100 mL) by solid‐phase extraction coupled with dispersive liquid–liquid microextraction and then analyzed using high performance liquid chromatography. Experimental variables including type and volume of elution solvent, volume and flow rate of sample solution, salt concentration, type and volume of extraction solvent and sample solution pH were investigated for the solid‐phase extraction coupled with dispersive liquid–liquid microextraction with these analytes, and the best results were obtained using methanol as eluent and ethylene chloride as extraction solvent. Under the optimal conditions, an exhaustive extraction for four analytes (recoveries >86.9%) and high enrichment factors were attained. The limits of detection were between 0.021 and 0.15 μg/L. The relative standard deviations for 0.5 μg/L of the pesticides in water were in the range of 1.9–6.8% (n = 5). The proposed strategy offered the advantages of simple operation, high enrichment factor and sensitivity and was successfully applied to the determination of four organophosphorus pesticides in water samples.     

Determination of some organophosphorus and azole group pesticides in water samples by dispersive liquid-liquid microextraction coupled with GC/MS

A dispersive liquid-liquid microextraction (DLLME) procedure coupled with GC/MS detection is described for preconcentration and determination of some organophosphorus and azole group pesticides from water samples. Experimental conditions affecting the DLLME procedure were optimized by means of an experimental design. A mixture of 60 microL chlorobenzene (extraction solvent) and 750 microL acetonitrile (disperser solvent), 3.5 min extraction time, and 7.5 mL aqueous sample volume were chosen for the best recovery by DLLME. The linear range was 1.6-32 microg/L. The LOD ranged from 48.8 to 68.7 ng/L. The RSD values for organophosphorus and azole group pesticides at spiking levels of 3, 6, and 9 microg/L in water samples were in the range of 1.1-12.8%. The applicability and accuracy of the developed method were determined by analysis of spiked water samples, and the recoveries of the analyzed pesticides from artesian, stream, and tap waters at spiking levels of 3, 6, and 9 microg/L were 89.3-105.6, 89.5-103.0, and 92.0-111.3%, respectively.