Comparison of Two Procedures for Extraction and Clean-up of Organophosphorus and Pyrethroid Pesticides in Sediment

Two procedures were compared for extraction and clean-up of 20organophosphorus and 19 pyrethroid pesticides in sediment to identify the more effective procedurefor groups of pesticides or individual compounds. In Procedure I, methanol/water and n-hexane wereused for extraction, and 1:10 (v/v) dichloromethane in n-hexane and acetone were used as eluents foreluting the analyte through the cartridge, with one evaporating steps on a rotary evaporator andtwo eluting steps on the cartridge. n-hexane/acetone (2:1, v/v) was used for extraction and elutionin Procedure II with one evaporating step on a rotary evaporator and one eluting step on thecartridge. All extractions were performed under an ultrasonic bath and gas chromatography and massspectrometry were utilized for measurements. Procedure II was developed as a rapid, timesaving, lesscostly and safer substitute for Procedure I which was an old method. Procedure II was moreeffective for almost all the organophosphorus pesticides tested and 11of the 19 pyrethroidpesticides, while Procedure I was more appropriate for analysis of 5 pyrethroid pesticides. However,recoveries of most pyrethroid pesticides were fairly low. Thus, further studies should focus onadjustment and formulation of solvents for more efficient extraction and clean-up of pyrethroidpesticides from sediment samples.

Application of Short Sequential Extraction Procedure(SSEP) for the Determination of Zn, Cu, and Cd Contents in Riverbed Sludge in Hejiagou, Harbin, China

A short sequential extraction procedure（SSEP） was applied to the determination of more readily available metal fractions of Zn, Cu, and Cd in the riverbed sludge in Hejiagou, Harbin, China. From the results, a potential order of metal availability in seven sludge samples was proposed： Cd 〈 Cu 〈 Zn, and samples S1 , S2, and S4 were used for the determination of total Zn content, and sample S3 used for the determination of total Cu content in the mobile and the mobilizable fractions showed the highest pollution risk. The results with regard to metal mobility in sludge samples were confirmed by the individual and global contamination factors that were calculated from the nonresidual and residual metal contents. The results obtained from metal-release experiments after exposure of sludge to environmental conditions agreed well with those obtained from both SSEP and the individual and global contamination factors, indicating that the maximum metal release could be an additional factor to evaluate the heavy metal availability in contaminated sludge. A substantial time saving was achieved by using the metal-release method in the present study.

Investigation on Fe,Mn,Zn,Cu,Pb and Cd fractions in the natural surface coating samples and surficial sediments in the Songhua River,China

Natural surface coating samples （NSCSs） from the surface of shingles and surficial sediments （SSs） in the Songhua River, China were employed to investigate the relationship between NSCSs and SSs in fractions of heavy metals （Fe, Mn, Zn, Cu, Pb, and Cd） using the modified sequential extraction procedure （MSEP）. The results show that the differences between NSCSs and SSs in Fe fi＇actions were insignificant and Fe was dominantly present as residual phase （76.22% for NSCSs and 80.88% for SSs） and Fe-oxides phase （20.33% for NSCSs and 16.15% for SSs）. Significant variation of Mn distribution patterns between NSCSs and SSs was observed with Mn in NSCSs mainly present in Mn-oxides phase （48.27%） and that in SSs present as residual phase （45.44%）. Zn, Cu, Pb and Cd were found dominantly in residual fractions （〉48%）, and next in solid oxides/hydroxides for Zn, Pb and Cd and in easily oxidizable solids/compounds form for Cu, respectively. The heavy metal distribution patterns implied that Fe/Mn oxides both in NSCSs and SSs were more important sinks for binding and adsorption of Zn, Pb and Cd than organic matter （OM）, and inversely, higher affinity of Cu to OM than Fe/Mn oxides in NSCSs and SSs was obtained. Meanwhile, it was found that the distributions of heavy metals in NSCSs and SSs were similar to each other and the pseudo-total concentrations of Zn, Cu, Pb and Cd in NSCSs were greater than those in SSs, highlighting the more importance for NSCSs than SSs in controlling behaviours of heavy metals in aquatic environments.

Phosphorus speciation in sediments of Lake Hongfeng, China

This study was conducted to evaluate the distribution characteristics of phosphorus and its species in 14 sediments samples collected from Lake Hongfeng based on sequential extraction. Lake Hongfeng, a major drinking-water source for Guiyang City in southwestern China, is one of the largest artificial reservoirs located in a typical karstic area of the Yunnan-Guizhou Plateau. The results of this study indicate that the average percentages of DP, Al-P, Fe-P, Ca-P and OP in the lake sediments were 0.52, 6.59, 6.09, 42.85 and 40.27, respectively. The concentrations of organic phosphorus (OP) were lower than those of inorganic phosphorus (IP), which consisted mainly of calcium-bound phosphorus (Ca-P). The high concentrations of Ca-P may temporarily control the release of phosphorus from the sediments because it is a relatively stable, inert, and non-bioavailable phosphorus fraction. However, a large number of phosphate solubilizing bacteria can transform insoluble phosphate into bioavailable forms. Moreover, the concentrations of total phosphorus (TP) in the lake sediments were high; thus, the potential for the release of phosphorus from the sediments to the water column and phosphorus bioavailability were still significant. Further statistical analyses of the results revealed significant correlations between phosphorus species in sediments from the lake with two extractable principal component species (PCs) and five selectable cluster levels allowing interpretation of possible origins of phosphorus loading and the release of phosphorus. Furthermore, available remediation measures were briefly assessed for the lake with consideration of its distinctive environmental features.

Fast Determination of Benzodiazepines in Human Urine via Liquid-Liquid Extraction with Low Temperature Partitioning and LC-HRMS

A simple and high-throughput method to simultaneously determine selected benzodiazepines (i.e., diazepam, lorazepam, clonazepam, and bromazepam) in urine was developed and validated. The entire methodology consisted of the application of an innovative extraction/cleanup procedure, namely liquid-liquid extraction with low-temperature partitioning (LLE-LTP), and analysis by liquid chromatography combined with high-resolution mass spectrometry (LC-HRMS). The LLE-LTP procedure was optimized via factorial design and by evaluating crucial variables, specifically the freezing mode (either slow or fast), the urine/acetonitrile volume ratio, and the sample ionic strength. The benzodiazepines were quantified using matrix-matched calibration curves where the following parameters were assessed by validation protocol: in general, linearity range of 17 - 200 μg?L–1 (r > 0.9957);limits of detection lower than 5 μg?L–1;relative standard deviations (RSD) lower than 12.5%;and accuracy ranging from 72.3 to 117%. To test this procedure’s performance, the method was applied to determine the content of diazepam in actual urine samples. The validation results obtained for the method demonstrated that the present methodology could be potentially applied in proficient laboratories as a routine approach for determining benzodiazepines compounds content in urine.

Performance of the procedure for ultra-rapid extraction and loop-mediated isothermal amplifcation (PURE-LAMP) method to detect malaria in Haiti

Background Malaria continues to cause burden in various parts of the world.Haiti,a Caribbean country,is among those aiming to eliminate malaria within a few years.Two surveys were conducted in Haiti during which we aimed to evaluate the performance of the simple and rapid procedure for ultra-rapid extraction-loop-mediated isothermal amplifcation(PURE-LAMP)method with dried blood spots as an alternative diagnostic method for malaria in the context of low to very low rates of transmission.Methods Febrile and afebrile people were recruited from three administrative divisions within Haiti:Nippes,Sud and Grand’Anse,during the summers of 2017(early August to early September)and 2018(late July to late August).Their blood samples were tested by microscopy,rapid diagnostic tests(RDT),PURE-LAMP and nested PCR to detect Plasmodium infection.Sensitivity,specifcity,positive and negative predictive values and kappa statistics were estimated with the nested PCR results as the gold standard.Results Among 1074 samples analyzed,a positive rate of 8.3%was calculated based on the nested PCR results.Among febrile participants,the rates in 2017 and 2018 were 14.6%and 1.4%,respectively.Three positives were detected among 172 afebrile participants in 2018 by PURE-LAMP and nested PCR,and all three were from the same locality.There was no afebrile participants recruited in 2017.The PURE-LAMP,RDT and microscopy had respective sensitivities of 100%,85.4%and 49.4%.All of the testing methods had specifcities over 99%.Conclusions This study confrmed the high performance of the PURE-LAMP method to detect Plasmodium infection with dried blood spots and recommends its use in targeted mass screening and treatment activities in low endemic areas of malaria.

Nutrient alterations following biochar application to a Cd-contaminated solution and soil

Biochars,when applied to contaminated solutions or soils,may sequester potentially toxic elements while releasing neces-sary plant nutrients.This purpose of this study focused on quantifying both phenomenon following wheat straw(Triticum aestivum L.)biochar application(0,5,and 15%by wt)to a Cd containing solution and a Cd-contaminated paddy soil using 240-day laboratory batch experiments.Following both experiments,solid phases were analyzed for elemental associations using a combination of wet chemical sequential extractions and synchrotron-based X-ray absorption spectroscopy(XAS).When wheat straw biochar was applied at 15%to Cd containing solutions,Cd and Zn concentrations decreased to below detection in some instances,Ca and Mg concentrations increased by up to 290%,and solution pH increased as compared to the 5%biochar application rate.Similar responses were observed when biochar was added to the Cd-contaminated paddy soil,suggesting that this particular biochar has the ability to sequester potentially toxic elements while releasing necessary plant nutrients to the soil solution.When significant,positive correlations existed between nutrient release over time,while negative correlations were present between biochar application rate,potentially toxic element sorption and pH.The latter suggests that potentially toxic elements were sorbed by a combination of organic functional groups or mineral precipitation based on whether pH was above or below~7.In support of this contention,the wet chemical sequential extraction procedure in conjunction with previously observed Cd or current Zn XAS showed that biochar application promoted the formation of layered double hydroxides,sorption to(oxy)hydroxides,and organically bound to biochar as Zn species.As a multi-functional material,biochar appears to play an important role in sequestering Cd while releasing essential plant nutrients.These findings suggest that biochar may be a‘win-win’for improving environmental quality in potentially toxic element contaminated agroecosystems.