Development of in-house ELISA for detection of chloramphenicol in bovine milk with subsequent confirmatory analysis by LC-MS/MS

This study was undertaken to develop and validate direct competitive ELISA for the determination of chloramphenicol residues in bovine milk. Antisera and an enzyme-tracer for chloramphenicol were prepared and used to develop an ELISA with inhibition concentrations, IC₂₀ and IC₅₀, of 0.09 and 0.44 ng mL^?1, respectively. Milk samples were spiked with standards equivalent to 0, 0.2, 0.3, 0.5, 1.0 &; 1.5 ng mL^?1 and extracted in methanol. The mean recoveries were found to be 73–100% with coefficient of variance 7–11%. The decision limit (CCα) and detection capability (CCβ) were calculated as 0.10 and 0.12 ng mL^?1, respectively. The results were found comparable with the commercial ELISA, having recoveries of 87 to 100%, CCα 0.09 ng mL^?1 and CCβ 0.12 ng mL^?1. As per Commission Decision 2002/657/EC, in-house ELISA was further validated by using LC-MS/MS. Mass spectral acquisition was done by using electrospray ionization in the negative ion mode applying single reaction monitoring of the diagnostic transition reaction for CAP (m/z 152, 194 and 257). The calibration curve showed good linearity in concentrations from 0.025 to 1.6 ng mL^?1 with correction coefficient 0.9902. The mean recoveries were found to be 88 to 100%. The CCα was calculated as 0.057 ng mL^?1 and CCβ 0.10 ng mL^?1. Since CCα and CCβ are less than half of the MRPL (0.15 ng mL^?1), the test was found suitable for screening and quantification of CAP residues in bovine milk samples. Results of surveillance studies indicated that out of 31 analyzed milk samples, 12.9% samples were found with CAP residues but only 3.2% samples were declared positive with maximum concentration 0.31 ng mL^?1, slightly above the MRPL.     

Extraction procedure optimization for perfluorooctane sulfonate and perfluorooctanoic acid in food packaging determination by LC-MS/MS

This research aimed to optimize the extraction method parameters for sample pretreatment and determine the levels of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) contamination in food packaging made of paper. Techniques used were pressurized liquid extraction (PLE) followed by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). Influence parameters of PLE were carefully evaluated for extracted concentration of samples in low level (ng g^?1). The study found that the optimal conditions for PLE were 30 min static extraction time with a flush volume of 100% cell volume and one extraction cycle at 80°C and 1,000 psi. The extraction technique validated the absolute recovery from PFOS and PFOA fortified control samples at three different levels (5, 50, and 200 ng g^?1), with seven repeats at each fortification level. The average recoveries were 79% or higher, with relative standard deviation (RSD) less than 11%. Optimization of the PLE method was established based on recovery data, accuracy, precision, and repeatability of the method. Using optimal PLE technique, PFOS and PFOA were extracted from 34 food-packaging samples collected in Thailand. PFOS and PFOA were detected in all kinds of collected samples, with average concentrations of 4.89 and 2.87 ng g^?1, respectively. The concentrations of PFOS and PFOA were highest in fast-food container samples: 36.99 and 9.99 ng g^?1, respectively.     

Bisphenol A and Bisphenol S release in milk under household conditions from baby bottles marketed in Italy

A simple and sensitive validated analytical method based on liquid chromatography coupled to tandem fluorescence (FD) and ultraviolet (UV) spectrophotometry was applied to monitor the presence of bisphenol A and bisphenol S in plastic baby bottles marketed in Italy. The limits of detection (LOD) were 3.75 ng mL^?1 and 80.00 ng mL^?1, and those of quantification (LOQ) were 12.51 ng mL^?1 and 260.00 ng mL^?1 for BPA (FD detection) and for BPS (UV detection), respectively. BPA was found in only four samples, two samples undergone to microwave heating and two samples undergone to bottle warmer heating either at 40°C or at 80°C. Although the quantities of leached BPA were well below the reference dose for daily intake established by the European Food Safety Authority (EFSA) (4.0 µg kg^?1 bw/day), the release of BPA and BPS from these plastic materials should be carefully considered by the government authorities to increase people's awareness on this issue and to protect the most vulnerable population group.     

Evaluation of potential genotoxic/cytotoxic effects induced by epoxiconazole and fenpropimorph-based fungicide in bovine lymphocytes in vitro

Potential genotoxic/cytotoxic effects of the epoxiconazole/fenpropimorph-based fungicide were investigated using single cell gel electrophoresis and cytogenetic assays: chromosomal aberrations, sister chromatid exchanges, micronuclei and fluorescence in situ hybridization in cultured bovine lymphocytes. No statistically significant elevations of DNA damage and increases in cytogenetic endpoints were seen. However, evident cytotoxic effect presented as a decrease in mitotic and proliferation indices were recorded after exposure of bovine lymphocytes to the fungicide for 24 and 48 h at concentrations ranging from 3 to 15 µg mL^?1 (P < 0.05, P < 0.01, P < 0.001). Similarly, for 24 h an inhibition in the cytokinesis block proliferation index (CBPI) was obtained after exposure to the fungicide at concentrations ranging from 1.5 to 15 µg mL^?1 (P < 0.01, P < 0.001) in each donor.     

Development of indirect competitive ELISA using egg yolk-derived immunoglobulin (IgY) for the detection of Gentamicin residues

Gentamicin (Gent) is an aminoglycoside antibiotic being used in livestock sector. Gent residues could cause some genetic disorders by nonsense mutations. This study aimed to develop IgY-based ELISA for the detection of Gent in animal products. Gent was conjugated with Bovine serum albumin (BSA) by carbodiimide method for further immunization in the laying chickens. PEG-6000 extraction method was employed to extract IgY from the egg yolk. The titer of anti-Gent-IgY attained the peak of 1:256,000 after the 5^th booster immunization. Checkerboard titration confirmed that, anti-Gent IgY in 1:2,000 dilution could give an Optical Density (OD) 1.0 at 2 µg mL^?1 of Gent-OVA coating concentration. IgY-based indirect competitive ELISA (Ic-ELISA) showed that, the IC₅₀ value of anti-Gent IgY was 2.69 ng mL^?1 and regression curve equation was y = ?16.27x + 56.97 (R² = 0.95, n = 3), confirming that, the detection limit (LOD, IC₁₀ value) was 0.01 ng mL^?1. Recoveries from fresh milk, pork and chicken samples were ranged from 69.82% to 94.32%, with relative standard deviation lower than 10.88%. Our results suggested that generated anti-Gent IgY antibodies can be used in routine screening analysis of Gent residues in food samples.     

Assessment of Organochlorine Pesticide Residues in Water,Sediment, and Fish of the Songhua River,China

This study examined residual concentrations and associated ecological risks of the organochlorine pesticides (OCPs) hexa- chlorocyclohexane (HCH) and dichloro-diphenyl-trichloroethane (DDT) in water, sediment, and fish of the Songhua River in Zhaoyuan County, China. In June 2012, 10 water, 10 sediment, and 20 fish samples were collected. Residual concentrations of ΣHCH and ΣDDT ranged from 10.0–35.59 ng L^?1 (mean 28.03 ± 11.66 ng L^?1) and 5.12–39.66 ng L^?1 (mean 32.36 ± 11.58 ng L^?1) for water. Residual concentrations of ΣHCH and ΣDDT ranged from 0.52–3.00 ng g^?1 (mean 2.04 ± 0.73 ng g^?1) and 0.34–3.41 ng g^?1 (mean 2.38 ± 0.92 ng g^?1) for sediment. The ratios of α-HCH/γ-HCH were close to 1 at the majority of sampling points, indicating considerable new pollution from the use of lindane. The ratios of p,p′-DDE + p,p′-DDD/ΣDDT were less than 0.5, indicating recent inputs from DDT impurities in dicofol. All HCH and DDT isomers except for p,p′-DDD were detected in fish tissue samples, but the associated ecological risks were estimated to be below levels of concern. The study revealed a historical usage of OCPs in the Zhaoyuan section of the Songhua River and new OCP from the use of lindane and dicofol.     

Determination of propineb and its metabolites propylenethiourea and propylenediamine in banana and soil using gas chromatography with flame photometric detection and LC–MS/MS analysis

A sensitive and specific method for the determination of propineb and its metabolites, propylenethiourea (PTU) and propylenediamine (PDA), using gas chromatography with flame photometric detection (GC-FPD) and LC–MS/MS was developed and validated. Propineb and its metabolite residue dynamics in supervised field trials under Good Agricultural Practice (GAP) conditions in banana and soil were studied. Recovery of propineb (as CS₂), PDA and PTU ranged from 75.3 to 115.4% with RSD (n = 5) of 1.3–11.1%. The limit of quantification (LOQ) of CS₂, PDA and PTU ranged from 0.005 to 0.01 mg kg^?1, and the limit of detection (LOD) ranged from 0.0015 to 0.0033 mg kg^?1. Dissipation experiments showed that the half-life of propineb in banana and soil ranged from 4.4 to 13.3 days. PTU was found in banana with a half-life of 31.5–69.3 days, while levels of PDA were less than 0.01 mg kg^?1 in banana and soil. It has been suggested that PTU is the major metabolite of propineb in banana. The method was demonstrated to be reliable and sensitive for the routine monitoring of propineb and its metabolites in banana and soil. It also serves as a reference for the detection and monitoring of dithiocarbamates (DTCs) residues and the evaluation of their metabolic pathway.     

In vitro toxicity of fungicides with different modes of action to alfalfa anthracnose fungus,Colletotrichum destructivum

Abstract

Sensitivity of 24 isolates of Colletotrichum destructivum O’Gara, collected from alfalfa plants in Serbia, to eight selected fungicides, was investigated in this study. Molecular identification and pathogenicity test of isolates tested were also performed. Fungicide sensitivity was evaluated in vitro, using mycelial growth assay method. All isolates exhibited significant pathogenicity, causing necrosis at the alfalfa seedling root tips two days after inoculation. Using the primer pair GSF1-SR1 and by comparing the amplified fragments of the tested isolates with the marker (M), the presence of the amplicon of the expected size of about 900?bp was determined for all isolates. The isolates tested in this study showed different sensitivity towards fungicides in vitro. Mycelial growth was highly inhibited by QoI (quinone outside inhibitors) fungicide pyraclostrobin (mean EC₅₀=0.39?µg mL^?1) and by DMI (demethylation-inhibiting) fungicide tebuconazole (mean EC₅₀=0.61?µg mL^?1), followed by azoxystrobin (mean EC₅₀=2.83?µg mL^?1) and flutriafol (mean EC₅₀=2.11?µg mL^?1). Multi-site fungicide chlorothalonil and MBC (methyl benzimidazole carbamate) fungicide thiophanate-methyl evinced moderate inhibition with mean EC₅₀=35.31 and 62.83?µg mL^?1, respectively. Thirteen isolates were sensitive to SDHI (succinate dehydrogenase inhibitors) fungicide boscalid and fluxapyroxad, (mean EC₅₀=0.49 and 0.19?µg mL^?1, respectively), while the rest of isolates were highly resistant.     

Novel pipette-tip graphene/poly (vinyl alcohol) cryogel composite extractor for the analysis of carbofuran and carbaryl in water

A novel pipette-tip extractor of a graphene/poly (vinyl alcohol) cryogel (graphene/PVA) composite sorbent was prepared to preconcentrate carbamate pesticides in environmental water samples before analysis with a gas chromatograph-flame ionization detector (GC-FID). This novel pipette-tip extractor with the graphene/PVA sorbent exhibited a high porosity when observed through a scanning electron micrograph (SEM). Under optimal conditions, using only 1.0 mL of sample and 0.75 mL of eluting solvent, the developed method provided a wide linear range of 10–700 ng mL^?1 and 10–500 ng mL^?1 with limit of detection (LOD) of 6.40 ± 0.18 and 9.17 ± 0.34 ng mL^?1 for carbofuran (2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate) and carbaryl (1-naphthyl methylcarbamate), respectively. The pipette-tip extractor provided high extraction efficiency with high accuracy indicated, by good recoveries in the range of 74.5 ± 4.8% to 119.7 ± 1.6% and 76 ± 15% to 114 ± 19% for carbofuran and carbaryl, respectively. In addition, the fabrication procedure showed a good pipette-tip extractor-to-pipette-tip extractor reproducibility with a relative standard deviation of 1.3–9.8% (n = 5). When the developed pipette-tip extractor was applied for the extraction of carbofuran and carbaryl in surface water samples near vegetable plantation areas, 25.9 ± 8.2 ng mL^?1 of carbofuran was found, and carbaryl was also detected in concentrations that ranged from 45.0 ± 4.0 to 191 ± 13 ng mL^?1.     

An LC-MS/MS method for creatine and creatinine analysis in paraquat-intoxicated patients

Abstract

A sudden increase in serum creatinine after paraquat intoxication has been reported in several clinical studies. However, this dramatic change of creatinine may be possibly due to an interconversion of creatine-creatinine in relation to paraquat toxicity. In order to investigate the creatine-creatinine relationship, a liquid chromatography tandem mass spectrometry in combination with electrospray ionization was developed and validated for simultaneous determination of creatine and creatinine in the serum. The chromatographic separation was achieved on a Gemini® C₆-Phenyl column with a gradient elution consisting of 0.1% formic acid in ultrapure water and methanol as the mobile phase. The method yielded suitable levels of specificity and selectivity, and calibration curves of creatine and creatinine in serum were linear over the concentration range of 0.5–200?µg mL^?1. The limit of quantification of both compounds was 0.5?µg mL^?1, and the method was accurate within the recovery range of 96.23–102.75%, indicating the robustness of the method. The method was successfully applied to toxicological samples from paraquat-intoxicated patients, and the concentrations of creatine and creatinine were quantified. High creatine concentrations in serum samples were observed which may lead to high serum creatinine despite normal kidney function as creatine is converted to creatinine in proportion to its concentration.     

Short chain nitrocompounds as a treatment of layer hen manure and litter; effects on in vitro survivability of Salmonella,generic E. coli and nitrogen metabolism

The current study was conducted to assess the bactericidal effectiveness of several nitrocompounds against pathogens in layer hen manure and litter. Evidence from an initial study indicated that treatment of layer hen manure with 12 mM nitroethane decreased populations of generic E. coli and total coliforms by 0.7 and 2.2 log₁₀ colony forming units (CFU) g^?1, respectively, after 24 h aerobic incubation at ambient temperature when compared to untreated populations. Salmonella concentrations were unaffected by nitroethane in this study. In a follow-up experiment, treatment of 6-month-old layer hen litter (mixed with 0.4 mL water g^?1) with 44 mM 2-nitroethanol, 2-nitropropanol or ethyl nitroacetate decreased an inoculated Salmonella typhimurium strain from its initial concentration (3 log₁₀ CFU g^?1) by 0.7 to 1.7 log₁₀ CFU g^?1 after 6 h incubation at 37°C in covered containers. After 24 h incubation, populations of the inoculated S. Typhmiurium in litter treated with 44 mM 2-nitroethanol, 2-nitropropanol, ethyl nitroacetate or nitroethane were decreased more than 3.2 log₁₀ CFU g^?1 compared to populations in untreated control litter. Treatment of litter with 44 mM 2-nitroethanol, 2-nitropropanol, ethyl nitroacetate decreased rates of ammonia accumulation more than 70% compared to untreated controls (0.167 µmol mL^?1 h^?1) and loses of uric acid (< 1 µmol mL^?1) were observed only in litter treated with 44 mM 2-nitropropanol, indicating that some of these nitrocompounds may help prevent loss of nitrogen in treated litter. Results warrant further research to determine if these nitrocompounds can be developed into an environmentally sustainable and safe strategy to eliminate pathogens from poultry litter, while preserving its nitrogen content as a nutritionally valuable crude protein source for ruminants.     

Study of spatial and temporal distribution of antimicrobial in water and sediments from caging fish farms by on-line SPE-LC-MS/MS

An on-line solid phase extraction liquid chromatography-tandem mass spectrometry (SPE-LC-MS/MS) method for the determination of 12 antimicrobials in sediment and surface water was developed and validated. Furthermore, the spatial and temporal antimicrobials distributions in the sediment and in the water of four fish farms located in the hydroelectric dam of Ilha Solteira Reservoir in Brazil were investigated over four seasons in three sampling sites: at the fish cages, 100 and 1,000 m downstream far from the cages. The method was performed using an Agilent Zorbax 80 SB-C8 column (9.4 × 15 mm, 5 µm) as the loading column, and the Agilent Zorbax Eclipse Plus C18 column (3.0 × 100 mm, 3.5 µm) as a separation column within a run time of 13 min. The limits of quantification were less than 9 ng·L^?1 for the antibiotics in water and 16 µg·kg^?1 in sediment; the recovery ranged from 80 to 119%, with a variation coefficient less than 11%, and the repeatability was lower than 15%. Oxytetracycline was found in the water in all sample seasons. However, florfenicol was identified in April and October 2013 and January 2014, and tetracycline was present in July 2013. Regarding the sediment, oxytetracycline and tetracycline were found in all sampling periods, but chlortetracycline was only identified in January 2014. The spatial distribution of antimicrobials showed that the main pollution source came from the fish farms. This study demonstrated that the proposed method is reliable for the monitoring of antimicrobials in water and sediments and it showed contamination in both matrices from Ilha Solteira Reservoir.     

Effect of Tinospora cordifolia on the reduction of ultraviolet radiation‐induced cytotoxicity and DNA damage in PC12 cells

The safety of Tinospora cordifolia and its potential to protect against ultraviolet radiation‐induced cytotoxicity and DNA damage in PC12 cells were investigated. To evaluate the safety of T. cordifolia, cell viability and agarose gel electrophoresis were carried out using PC12 cells treated with 0 to 100 μg mL^?1 of methanol extract of T. cordifolia. T. cordifolia extracts did not show cytotoxicity ranging 0 to 100 μg mL^?1. In addition, T. cordifolia extracts significantly increased cell viability at 1 ng, 10 ng and 1 μg mL^?1 concentrations in serum‐deprived medium compared to control. To confirm the protective role against UV‐induced damage, PC12 cells alone or in the presence of 10 ng, 100 ng, or 1 μg mL^?1 of T. cordifolia extract were exposed to 250, 270 and 290 nm of UV radiation, which corresponded to doses of 120, 150 and 300 mJ cm^?2, respectively. Treatment with T. cordifolia extracts significantly increased the cell survival rate irradiated at 290 nm. In addition, T. cordifolia extracts significantly reduced cyclobutane pyrimidine dimer formation induced by UV irradiation at all wavelengths. In conclusion, T. cordifolia is not toxic and safe for cells. Our findings can support its application as phototherapy in the medical sector.     

Development of a sensitive,competitive, indirect ELISA for the detection of fumonisin B1 in corn originating from Anhui province,China

Fumonisin B₁ (FB₁) is a secondary metabolite produced by Fusarium verticillioides or Fusarium proliferatum, which present in food and feed. It causes hazardous effects on human and animal health. A monoclonal antibody (mAb) against FB₁ was produced and a simple, reliable and sensitive, competitive, indirect enzyme-linked immunosorbent assay (ci-ELISA) for detection of FB₁ was developed and the experiment conditions were optimized. The coating concentration of FB₁-ovalbumin (FB₁-OVA) was 500 ng mL^?1, the action concentrations of anti-FB₁ mAb and goat anti-mouse IgG were 1.28 × 10⁴ and 1:5000, respectively. The 50% inhibitory concentration (IC₅₀) was 11 ng mL^?1, with a detectable range of 1.25–250 ng mL^?1, and a limit of determination (LOD) of 1.15 ng mL^?1. The cross-reactivity (CR) of the antibody against fumonisin B₂ (FB₂) was 60.4, and <1% against deoxynivalenol (DON), aflatoxin B₁ (AFB₁), ochratoxin A (OTA) or zearalenone (ZEN). In spiked samples (250 ng g^?1, 500 ng g^?1, 1000 ng g^?1), the mean recoveries ranged from 86.7 ± 5% to 102 ± 4%, and the coefficient of variation (CV) ranged from 3% to 10%. A survey of 96 corn samples from Bozhou, Fuyang, Bengbu, and Hefei, in Anhui province, China, was performed. Frequencies of FB₁ contamination were 83.3%, 95.8%, 20.8% and 91.7%, and the mean concentrations of positive samples were 0.702 μg kg^?1, 0.883 μg kg^?1, 0.074 μg kg^?1, and 0.276 μg kg^?1, respectively. The results of this study suggest that the ci-ELISA developed in this study can be used to identify FB₁ in corn, furthermore, further study is needed to investigate FB₁ contamination in food and feed to prevent its harmful health effects.     

Concentrations and distributions of 18 organochlorine pesticides listed in the Stockholm Convention in surface sediments from the Liaohe River basin,China

Organochlorine pesticides (OCPs) were analyzed in 26 surface sediment samples from the Liaohe River basin, and the distributions of and potential environmental risks posed by OCPs in the basin were evaluated. Eighteen OCPs listed in the Stockholm Convention were determined using isotope-dilution gas chromatography–high resolution mass spectrometry. This is the first study of hexachlorobenzene (HCB) in the Liaohe River basin sediments. The total OCP concentrations were 0.39–68.06 ng g^?1 dry weight. The total α-, β-, γ-, and δ-hexachlorocyclohexane (HCH), the total dichlorodiphenyltrichloroethane (DDT – p,p′-dichlorodiphenyldichloroethane (DDD), p,p′-dichlorodiphenyldichloroethylene (DDE), o,p^'-DDT, and p,p′-DDT), and the HCB concentrations in the sediment samples were 0.1–28.48 ng g^?1 (mean 4.01 ng g^?1), 0.08–6.52 ng g^?1 (mean 3.07 ng g^?1), and 0.18–24.8 ng g^?1 (mean 4.38 ng g^?1), respectively. The HCB concentrations were higher than the concentrations of the other OCPs, and the HCHs and HCB together were the dominant OCPs. β-HCH was the most abundant HCH isomer. The concentrations of DDTs and other OCPs were relatively low, and the (DDE+DDD)/DDT ratios (>0.5) and DDD/DDE ratios (<1) indicated that no recent DDT inputs had occurred in the Liaohe River system. The main sources of HCHs were probably the historical production and agricultural use of HCH in the study area. The DDT and HCH concentrations were generally below or similar to the concentrations that have been found in other parts of the world. An ecotoxicological evaluation indicated that HCHs in surface sediments pose slight risks to human and ecological health in the Liaohe River basin.     

Development,validation, and application of a method for the GC-MS analysis of fipronil and three of its degradation products in samples of water,soil, and sediment

A method for the identification and quantification of pesticide residues in water, soil, and sediment samples has been developed, validated, and applied for the analysis of real samples. The specificity was determined by the retention time and the confirmation and quantification of analyte ions. Linearity was demonstrated over the concentration range of 20 to 120 µg L^?1, and the correlation coefficients varied between 0.979 and 0.996, depending on the analytes. The recovery rates for all analytes in the studied matrix were between 86% and 112%. The intermediate precision and repeatability were determined at three concentration levels (40, 80, and 120 µg L^?1), with the relative standard deviation for the intermediate precision between 1% and 5.3% and the repeatability varying between 2% and 13.4% for individual analytes. The limits of detection and quantification for fipronil, fipronil sulfide, fipronil-sulfone, and fipronil-desulfinyl were 6.2, 3.0, 6.6, and 4.0 ng L^?1 and 20.4, 9.0, 21.6, and 13.0 ng L^?1, respectively. The method developed was used in water, soil, and sediment samples containing 2.1 mg L^?1 and 1.2% and 5.3% of carbon, respectively. The recovery of pesticides in the environmental matrices varied from 88.26 to 109.63% for the lowest fortification level (40 and 100 µg kg^?1), from 91.17 to 110.18% for the intermediate level (80 and 200 µg kg^?1), and from 89.09 to 109.82% for the highest fortification level (120 and 300 µg kg^?1). The relative standard deviation for the recovery of pesticides was under 15%.     

Ultra trace simultaneous determination of 50 polycyclic aromatic hydrocarbons in biota using pMRM GC-MS/MS

Abstract

A saponification extraction method with gas chromatography pseudo-MRM (pMRM) mass spectrometry detection was developed for the determination of 50 total polycyclic aromatic hydrocarbons (TPAH50, a combination of parent and alkylated homologues) in biota. The method was aimed at monitoring and identification of potential TPAH contaminants in bitumen impacted environments. Alkylated PAHs were determined by multi-level, quantitative calibration using parent PAHs. The developed and thoroughly validated method required only one injection for TPAH50 analysis which represents significant saving of time and expensive authentic alkylated standards. The current method was tested with certified reference mussel tissue NIST 1974c and performed well. In a comparison study, the method reached a limit of quantitation (LOQ) for the TPAH50 between 0.1 and 0.2?ng g^?1, while the QuEChERs enhanced matrix removal – lipid (EMR) kit produced by Agilent showed an LOQ of 5–10?ng g^?1. The current method relied on response factors (RF) for the quantitation of alkylated PAHs determined against parent PAHs. These RFs were shown to be stable and consistent over the course of 1 year, during which over 200 routine environmental biota monitoring samples were analyzed. The environmental biota monitoring samples analyzed include muscle, carcass and liver, with an average total PAH50 concentration of 13, 90 and 135?ng g^?1, respectively. Results show significant differences in the distributions of 1 ringed, 2 ringed, 3 ringed, 4 ringed, and 5+ ringed TPAHs between the types of biota samples.     

Analysis of Herbicide Krovar I™ by Liquid Chromatography with Atmospheric Pressure Chemical Ionization Mass Spectrometry

Abstract

A simple, very efficient method is presented for routine analysis of herbicide Krovar I? (active components bromacil and diuron) in water and soil samples. Water samples were extracted by liquid–liquid extraction with dichloromethane (DCM) as extraction solvent. For soil samples two different extraction techniques were compared: microwave-assisted solvent extraction and a shaking technique using a platform shaker. Extracts were analyzed by high performance liquid chromatography using a water:methanol gradient. Liquid chromatography was coupled with atmospheric pressure chemical ionization mass spectrometry (LC-APCI-MS) for quantification of bromacil and diuron. Optimization of the APCI-MS was done by using standards in the flow injection analysis mode (FIA). Method detection limit for liquid samples for bromacil is 0.04 µg L^?1 and for diuron 0.03 µg L^?1. Method detection limit for soil samples is 0.01 µg g^?1 dry weight for both compounds. Results of analysis of field samples of water and soil are also presented.     

Genotypic Differences in Effects of Cadmium Exposure on Plant Growth and Contents of Cadmium and Elements in 14 Cultivars of Bai Cai

Abstract

Fourteen cultivars of bai cai (Brassica campestris L. ssp. chinensis var. communis) were grown in the nutrient solutions containing 0–0.5 μg mL^?1 of cadmium (Cd) to investigate genotypic differences in the effects of Cd exposure on the plant growth and uptake and distribution of Cd in bai cai plants. The Cd exposure significantly reduced the dry and fresh weights of roots and shoots, the dry weight ratio of shoot/root (S/R), total biomass, and chlorophyll content (SPAD value). Cd concentrations in bai cai ranged from 13.3 to 74.9 μg g^?1 DW in shoots and from 163.1 to 574.7 μg g^?1 DW in roots under Cd exposure, respectively. The considerable genotypic differences of Cd concentrations and accumulations in both shoots and roots were observed among 14 bai cai cultivars. Moreover, Cd mainly accumulated in the roots. Cd also caused the changes of uptake and distribution of nutrients in bai cai and under the influence of cadmium, the concentration of potassium (K) decreased in shoot and increased in root. However, the concentrations of magnesium (Mg), phosphorus (P), manganese (Mn), boron (B), and iron (Fe) increased in shoots and decreased in roots. In addition, Cd exposure resulted in an increase in calcium (Ca), sulphur (S), and zinc (Zn) concentrations in both shoots and roots but had no significant effects on the whole uptake of the examined mineral nutrients except for S.     

A rapid and sensitive fluoroimmunoassay based on quantum dot for the detection of chlorpyrifos residue in drinking water

A rapid and sensitive indirect competitive fluorescence-linked immunosorbent assay (cFLISA) method based on quantum dots as the fluorescence label coupled with secondary antibody (Ab₂) for the detection of chlorpyrifos in drinking water has been developed. The cFLISA method allowed for chlorpyrifos determination in a liner working range of 15.2–205.5 ng mL^?1. The 50 % inhibition value (IC₅₀) and the limit of detection (LOD) of the cFLISA were 50.2 ng mL^?1 and 8.4 ng mL^?1, while the IC₅₀ and the LOD of the conventhional enzyme linked immunosorbent assay (ELISA) were 95.3 ng- mL^?1 and 16.2 ng mL^?1, respectively. When the concentrations of chlorpyrifos were 200, 100 and 50 ng mL^?1, the recoveries ranged from 90.8 % to 108.2 % with a coefficient of variation (CV) of 7.5 %–15.2 %. In water sample analysis, the results of cFLISA were similar to those obtained from a cELISA and a high performance liquid chromatography (HPLC) method, while the detection time by cFLISA was reduced 0.5 h compared with ELISA. It showed that cFLISA could be used as a new screening method for the detection of pesticide residue.