Direct qualitative and quantitative determination methodology for massive screening of DON in wheat flour based on multi-molecular infrared spectroscopy (MM-IR) with 2T-2DCOS.

Deoxynivalenol (DON) contamination in wheat flour induces a number of adverse health effects to consumers and livestock, even at very low concentrations. Direct detection methods for massive screening of DON in wheat flour is still lacking. A new methodology integrating multi-molecular infrared spectroscopy (MM-IR) with two-trace two-dimensional correlation spectroscopy (2T-2DCOS) was developed for in-situ qualitative and quantitative determination of DON in wheat flour as a whole. Typical spectral variation of wheat flour samples with diverse concentration of DON were stepwise characterized by MM-IR and tiny spectral profile differences resulting from concentration variation of DON were visually disclosed by 2T-2DCOS. Based on the obtained key spectral features of DON, 180 of wheat flour samples with DON higher and lower than 1.00 mg/kg were undoubtedly classified by Principal Component Analysis (PCA) and Support Vector Machines (SVM) with an accuracy rate up to 100% (for Second derivative spectra consisted of selected bands, SD-SS). Furthermore, a robust quantitative prediction model was established based on partial least squares (PLS) of SD-SS (Rc: 0.998, RMSEC: 0.135; Rp: 0.968, RMSEP: 0.421), and its excellent predictive capacity of model was validated by both residual prediction deviation (RPD) value of 3.2 and t-test. It was demonstrated that the developed methodology was applicable for screening and quantitative detection of DON in wheat flour based on the novel correlation analysis methods (SD-2DCOS-IR and 2T-2DCOS-IR) with chemometrics tools, which could be utilized both at laboratory and industrial level for quality control purposes of a large wheat flour sample set.

[Identify the Nitrate Sources in Different Land Use Areas Based on Multiple Isotopes].

Different land uses have different impacts on the water quality of the region. Multiple isotopes (δD-H2O, δ18O-H2O, δ15N-NO3-, and δ18O-NO3-) and the SIAR (stable isotope analysis in R) model were applied to identify the nitrate sources and estimate the proportional contributions of multiple nitrate sources in a river in a typical urban area (the Grand Canal, Hangzhou) and a river in a typical forest and agricultural area (Yuying Riveri). The results indicated that there were different degrees of nitrogen pollution in the Grand Canal and Yuying River; NO3--N and NH4+-N are the predominant forms of nitrogen in the Grand Canal, and the primary form of nitrogen in Yuying River was NO3--N. There was an obvious linear relationship between the hydrogen and oxygen isotopes (R2=0.78). The δD-H2O and δ18O-H2O values for the Grand Canal and Yuying River were distributed along the local meteoric waterline, indicating that precipitation served as the primary water source in these rivers. All of the δ18O-NO3- values of the Grand Canal and Yuying River were lower than 15 ‰. It was revealed that nitrification, rather than denitrification, was the primary N cycling process in the two rivers. The δ15N-NO3-/δ18O-NO3- ratios of some of the samples from the Grand Canal ranged from 1.3 to 2.1, accompanied by low concentrations of DO and NO2-, indicating that denitrification existed in some sections of the Grand Canal. The δ15N-NO3- values of the samples from the Grand Canal (average:6.1‰) were higher than those from the Yuying River (average:2.3‰). The NO3- source contributions differed significantly between the Grand Canal and Yuying River. The contributions of NO3- sources in the Grand Canal were sewage/manure (37.0%) > soil nitrogen (35.7%) > chemical fertilizer (19.1%) > precipitation (8.2%), and those in the Yuying River were chemical fertilizer (46.1%) > soil nitrogen (22.8%) > precipitation (17.3%) > sewage/manure (13.8%). The contribution of the sewage/manure was substantially increased in the Grand Canal in the urban area with stronger human activities primarily due to the sporadic discharge of domestic sewage and urban runoff. Chemical fertilizer is the main NO3- source in the Yuying River near the forest and agricultural area, suggesting that the nitrogen pollution caused by agricultural non-point sources was extremely serious. The contribution of precipitation decreased in the areas of substantial human activities. The isotopic fractionation produced by denitrification was affected by the contributions of the NO3- sources, which were calculated by SIAR model. Sewage/manure and chemical fertilizer produced significant impacts, followed by soil nitrogen and precipitation.

EDTA-enhanced phytoremediation of heavy metals from sludge soil by Italian ryegrass (Lolium perenne L.).

Landscaping of sludge is a kind of recycling disposal, but the potential heavy metal risks limit its application. In this paper, the sludge soil was remediated by ryegrass, and the effect of ethylene diamine tetraacetic acid (EDTA) was studied through pot experiments. Italian ryegrass was planted in the sludge soil treated with six gradients concentrations of 0, 1, 2, 3, 4, 5 mmol kg-1 of EDTA, and the planting conditions were kept the same. After 45 days of planting, compared with the control group (without EDTA treated), the application of 1-5 mmol kg-1 EDTA decreased ryegrass biomass by 2-43%, reduced soil pH value by 0.21-0.34 unit, and reduced 4.1-9.7% capacity of exchange cation, but increased 1.4-8.6% soil organic matter. After growing ryegrass, the contents of heavy metals decreased by 10% for Cu, 15% for Zn, 6% for Ni, 14% for Cd and 44% for Pb; and after spraying EDTA decreased again by 33% for Cu, 31% for Zn, 56% for Ni, 24% for Cd, and 68% for Pb. In ryegrass, the uptake heavy metals were enhanced, and bio-concentration factor of Cu, Zn, Ni, Cd, and Pb of EDTA treated groups were 1.9, 1.6, 4.1, 2.7, and 4.8 times of the control group, respectively. However, EDTA only significantly increased transfer factor values of Cu and Zn, and made bio-extraction factor value of Cu greater than 1. The remediation factor values were used to comprehensive assess accumulation capacity of heavy metals by ryegrass under EDTA treating, and they ordered in Zn > Cu > Ni > Cd > Pb, and the best dose was 2 mmol kg-1 EDTA. Prediction models for bio-concentration factor were established by using stepwise multiple linear regression, explaining 94.9-99.3% of the corresponding elements with soil organic matter, EDTA dosage, and/or pH value (p < 0.005). This paper provided effective heavy metals remediation data for municipal sludge landscape and the prediction models.

[Contribution of Nitrogen Sources in Water Sources by Combining Nitrogen and Oxygen Isotopes and SIAR].

It is very important to identify nitrate sources in reservoirs that serve as high quality water sources to control its eutrophication. Stable isotopes (δ15 N and δ18O) and a Bayesian model (stable isotope analysis in R, SIAR) were applied to identify nitrate sources and estimate the proportional contributions of multiple nitrate sources in four reservoirs (Qingshan reservoir, Duihekou reservoir, Siling reservoir, and Lifan reservoir) that serve as sources of drinking water in the Hangjiahu area, one of the most densely populated and most quickly developing areas in East China. It was shown that nitrogen pollution, which was dominated by nitrate (NO3-), existed in the four reservoirs. Greater human activities caused more nitrogen pollution (average NO3- concentration 0.21 mmol ·L-1) in the Qingshan reservoir. A significant positive correlation (P<0.01) was observed between Cl- and NO3-. The analysis of the water in the Duihekou reservoir, Siling reservoir, and Lifan reservoir, with lower Cl- concentrations and higher NO3-/Cl- ratios, suggested that chemical fertilizer was the main source, while the analysis of the water in the Qingshan reservoir, with medium Cl- concentrations and NO3-/Cl- ratios, indicated a mixture of NO3- sources. The δ15 N ranged from 0.9‰ to 7.2‰, and the δ18O ranged from 2.8‰ to 14.1‰ in the four reservoirs. The δ18O values in more than 86% of the water samples were less than 10‰, and the δ15 N/δ18O values in 93% of the water samples were less than 1.3. It was identified that nitrification rather than denitrification acted as the primary N cycling process in the four reservoirs. SIAR was used to estimate the proportional contribution of five NO3- sources (industrial wastewater, sewage/manure, chemical fertilizer, soil nitrogen, and precipitation) in the Qingshan reservoir and of three NO3- sources (chemical fertilizer, soil nitrogen, and precipitation) in the Duihekou reservoir, Siling reservoir, and Lifan reservoir. The source apportionment results showed that chemical fertilizers and soil nitrogen were the dominant nitrate sources and their contributions were 75%-82%. It was revealed that nitrogen pollution in the water source reservoir caused by cropping non-point source pollution was very serious. Nitrate source contributions in Qingshan reservoir also included sewage/manure (25%), soil nitrogen (7%), and precipitation (6%), indicating that nitrogen pollution by sewage/manure should not be ignored in the higher human activity areas. The nitrate source in the Duihekou reservoir, Siling reservoir, and Lifan reservoir also included precipitation, with the nitrate contribution from precipitation at 21%, 24%, and 15%, respectively. It was suggested that precipitation contributed more nitrate to the water in areas with less human activity.

[Nitrate Source Identification and Nitrification-denitrification at the Sediment-water Interface].

Identifying nitrate sources and its transformation mechanisms are important for nitrate pollution control in surface water. The columnar core sediment samples in West Lake were taken in different seasons. The transformation of nitrogen at the sediment-water interface was studied using nitrogen and oxygen isotopes, stable isotope analysis in R (SIAR) and acetylene inhibition method in the West Lake, Hangzhou. The results showed that the concentration gradient of both NO3-and NH4+ existed at the sediment-water interface. NO3- concentrations decreased from bottom water to pore water and NO3- was accumulated in sediments. NH4+ concentrations increased from bottom water to pore water and NH4+ was released from sediments. Nitrate sources in bottom water where nitrification exited were sewage (manure), soil nitrogen, chemical fertilizer and precipitation. Sewage (manure) was the major nitrogen contributor (60.8%) in summer. Particularly high δ15 N values in pore water indicated that there was strong denitrification at the sediment-water interface in West Lake. The average nitrification rate and denitrification rate at the sediment-water interface were 2.85 mmol·(m2·d)-1 and 23.51 µmol·(m2·d)-1, respectively. The sediment-water interface played a role in nitrogen removal process in aquatic environment. Seasonal and spatial variations of nitrification rates and denitrification rates were found in this study. Temperature and dissolved oxygen were the main influential factors for the transformation of nitrogen at the sediment-water interface in West Lake.

Assessment of lead bioaccessibility in soils around lead battery plants in East China.

Soil ingestion is an important human exposure pathway for lead (Pb). A modified physiologically based extraction test was applied to 70 soil samples from five battery plants in East China. The mean values for soil pH, soil organic matter, Fe and Mn concentrations ranged from 5.9% to 8.1, 0.37% to 2.2%, 2.78% to 3.75%, and 507-577 mg kg(-1), respectively, while Pb concentrations ranged widely in 14.3-2000 mg kg(-1). The isotopic ratios of 14 soils from one of the five battery plants formed a straight line in the plot of (208)Pb/(206)Pb vs. (207)Pb/(206)Pb, indicating Pb emissions from the lead battery plant as the dominant anthropogenic source within 200 m. Lead bioaccessibility in the soils ranged from 4.1% to 66.9% in the gastric phase and from 0.28% to 9.29% in the gastrointestinal phase. Multiple step regressions identified modes as BAgastric=-106.8+0.627[Pb]+19.1[Fe]+11.3[SOM], and BAgastrointestinal=-2.852+0.078[Pb].

[Metal ions restrain the elimination of 4-tert-octylphenol by delta-MnO2].

The effect of metal ions on elimination of 4-t-OP by synthetic delta-MnO2 suspension at pH 4.0 was studied. Experiments indicated that the removal of 4-t-OP by delta-MnO2 achieved 100% at reaction time of 150 min. However, the removal of 4-t-OP by delta-MnO2 was restrained when metal ions were added, and the higher concentration of metal ion was, the stronger the inhibition produced. Additionally, there were apparent differences among the inhibitory effect of the tested metal ions. Firstly, Pb2+ and Mn2+ had the strongest effect at pH 4.0, followed by the transition metal ions, then the alkaline earth ions, while the alkali metal ions had little influence on the removal of 4-t-OP by delta-MnO2. Also comparing the adsorption results of metal ions by delta-MnO2, Pb2+ showed the greatest attraction with delta-MnO2, and among the other metal ions, transition metal ions were adsorbed a little more strongly on delta-MnO2 than alkaline earth metal ions. Consequences showed that the inhibitory effects of metal ions were due to their occupying reactive sites on delta-MnO2 surface, which competed with 4-t-OP. Moreover, the dissimilar suppressions were contributed by the different adsorption capacities, surface structure change of MnO2 and the difference of free metal ion percentage in solution as well as metal ions radii.

Time-dependent movement and distribution of chlorothalonil and chlorpyrifos in tomatoes.

Determining the distribution of pesticides in fruits is essential to eliminate pesticide residues during food processing. In this study, the dynamic distribution of two pesticides, chlorothalonil (CHT) and chlorpyrifos (CHP), were determined in different tomato parts following immersion in pesticide solutions. The concentrations of CHT and CHP in tomato followed an order of cuticle>plasma>pulp. However, the plasma initially accumulated the highest pesticide concentration. And the ratio of CHT concentration to that of CHP in plasma was about 2.1:1, similar to the ratio in solution, which suggested carpopodium as the entry site for the pesticides tested. The ratio in the cuticle was 0.02:1-0.06:1. This was consistent with the ratio of Kow for the two pesticides, manifesting the direct pesticide transfer from solution to cuticle. Following pesticide injection into tomato, the degradation of CHT over 96h was described by a first-order decay equation, Ctomato(t)CHT=C0×e(-0.0239t). The CHP concentration in tomato remained nearly constant with little degradation detected. Deducting the amount of degradation and migration, volatilization appeared to contribute the most amount of migration of CHT and CHP in tomato.

Natural and anthropogenic lead in soils and vegetables around Guiyang city, southwest China: a Pb isotopic approach.

Soils, vegetables and rainwaters from three vegetable production bases in the Guiyang area, southwest China, were analyzed for Pb concentrations and isotope compositions to trace its sources in the vegetables and soils. Lead isotopic compositions were not distinguishable between yellow soils and calcareous soils, but distinguishable among sampling sites. The highest (207)Pb/(206)Pb and (208)Pb/(206)Pb ratios were found for rainwaters (0.8547-0.8593 and 2.098-2.109, respectively), and the lowest for soils (0.7173-0.8246 and 1.766-2.048, respectively). The (207)Pb/(206)Pb and (208)Pb/(206)Pb ratios increased in vegetables in the order of roots

Altered transfer of heavy metals from soil to Chinese cabbage with film mulching.

The influence of film mulching on the migration of metals from soil to cabbage was investigated. Following a 50-day growth in field plots mulched or unmulched, root-zone soils and Chinese cabbage (Brassica chinensis L.) were sampled for metal analysis. Mulching slightly decreased the soil mobile (acid-extractable) Cd, but increased its transfer from root to the cabbage parts. As an essential element, Cu was readily transferred to the cabbage parts. While mulching decreased the soil mobile Zn, reduced soil pH resulted in its enhanced soil-to-root migration. This, however, did not increase the transfer of Zn within cabbage. Although mulching increased the soil mobile Pb by 200%, an increase in Pb in cabbage leaves but a decrease in stem result presumably from the enhanced foliar uptake of atmospheric Pb. This study suggests that mulching may promote the accumulation of toxic metals such as Cd and Pb in cabbage and therefore increase crop risks to human health.

[Evaluation of phytoavailability of zinc and cadmium in contaminated soils by a short sequential extraction procedure].

Cultivated soils and maize samples from heavy metal contaminated locations affected by zinc smelting activities were collected in Hezhang County, Guizhou Province. Chemical fractions of zinc and cadmium (extracted by 0.01 mol x L(-1) CaCl2 and 0.005 mol x L(-1) DTPA) were evaluated by using a short three-step sequential extraction procedure. Results showed that Zn and Cd in soil were dominated by residual fraction, while the CaCl2 extractable and DTPA extractable fraction are only accounted for 0.63%, 3.91% for Zn, and 10.94%, 10.13% for Cd, respectively. Correlation analyses demonstrated that soil CaCl2 extractable metals were not correlated with maize metal concentrations, whereas the DTPA extractable fraction, residual fraction and total Zn and Cd concentrations were correlated significantly with the metal concentrations in maize roots, stems and leaves. These results indicated that CaCl2 extractable fraction may not pay important role on metal phytoavailability in the studied soils. While DTPA extractable fraction and total metal concentrations can be employed to evaluate metals phytoavailability.