Evaluation of in Situ DGT Measurements for Predicting the Concentration of Cd in Chinese Field-Cultivated Rice: Impact of Soil Cd:Zn Ratios

DGT (diffusive gradients in thin-films) has been proposed as a tool for predicting Cd concentrations in rice grain, but there is a lack of authenticating data. To further explore the relationship between DGT measured Cd and concentrations in rice cultivated in challenging, metal degraded, field locations with different heavy metal pollutant sources, 77 paired soil and grain samples were collected in Southern China from industrial zones, a "cancer village" impacted by mining waste and an organic farm. In situ deployments of DGT in flooded paddy rice rhizospheres were compared with a laboratory DGT assay on dried and rewetted soil. Total soil concentrations were a very poor predictor of plant uptake. Laboratory and field deployed DGT assays and porewater measurements were linearly related to grain concentrations in all but the most contaminated samples where plant toxicity occurred. The laboratory DGT assay was the best predictor of grain Cd concentrations, accommodating differences in soil Cd, pollutant source, and Cd:Zn ratios. Field DGT measurements showed that Zn availability in the flooded rice rhizospheres was greatly diminished compared to that of Cd, resulting in very high Cd:Zn ratios (0.1) compared to commonly observed values (0.005). These results demonstrate the potential of the DGT technique to predict Cd concentrations in field cultivated rice and demonstrate its robustness in a range of environments. Although, field deployments provided important details about in situ element stoichiometry, due to the inherent heterogeneity of the rice rhizosphere soils, deployment of DGT in dried and homogenized soils offers the best possibility of a soil screening tool.

An arsenic-contaminated field trial to assess the uptake and translocation of arsenic by genotypes of rice

Compared to other cereals, rice has particular strong As accumulation. Therefore, it is very important to understand As uptake and translocation among different genotypes. A field study in Chenzhou city, Hunan province of China, was employed to evaluate the effect of arsenic-contaminated soil on uptake and distribution in 34 genotypes of rice (including unpolished rice, husk, shoot, and root). The soil As concentrations ranged from 52.49 to 83.86 mg kg-1, with mean As concentration 64.44 mg kg-1. The mean As concentrations in rice plant tissues were different among the 34 rice genotypes. The highest As concentrations were accumulated in rice root (196.27-385.98 mg kg-1 dry weight), while the lowest was in unpolished rice (0.31-0.52 mg kg-1 dry weight). The distribution of As in rice tissue and paddy soil are as follows root » soil > shoot > husk > unpolished rice. The ranges of concentrations of inorganic As in all of unpolished rice were from 0.26 to 0.52 mg kg-1 dry weight. In particular, the percentage of inorganic As in the total As was more than 67 %, indicating that the inorganic As was the predominant species in unpolished rice. The daily dietary intakes of inorganic As in unpolished rice ranged from 0.10 to 0.21 mg for an adult, and from 0.075 to 0.15 mg for a child. Comparison with tolerable daily intakes established by FAO/WHO, inorganic As in most of unpolished rice samples exceeded the recommended intake values. The 34 genotypes of rice were classified into four clusters using a criteria value of rescaled distance between 5 and 10. Among the 34 genotypes, the genotypes II you 416 (II416) with the lowest enrichment of As and the lowest daily dietary intakes of inorganic As could be selected as the main cultivar in As-contaminated field.

Application of factor analysis and geostatistics to identify processes controlling the distribution and bioaccessibility of trace elements in Northern Ireland soils

Geologic and environmental factors acting over varying spatial scales can control
trace element distribution and mobility in soils. In turn, the mobility of an element in soil will affect its oral bioaccessibility. Geostatistics, kriging and principal component analysis (PCA) were used to explore factors and spatial ranges of influence over a suite of 8 element oxides, soil organic carbon (SOC), pH, and the trace elements nickel (Ni), vanadium (V) and zinc (Zn). Bioaccessibility testing was carried out previously using the Unified BARGE Method on a sub-set of 91 soil samples from the Northern Ireland Tellus1 soil archive. Initial spatial mapping of total Ni, V and Zn concentrations shows their distributions are correlated spatially with local geologic formations, and prior correlation analyses showed that statistically significant controls were exerted over trace element bioaccessibility by the 8 oxides, SOC and pH. PCA applied to the geochemistry parameters of the bioaccessibility sample set yielded three principal components accounting for 77% of cumulative variance in the data
set. Geostatistical analysis of oxide, trace element, SOC and pH distributions using 6862 sample locations also identified distinct spatial ranges of influence for these variables, concluded to arise from geologic forming processes, weathering processes, and localised soil chemistry factors. Kriging was used to conduct a spatial PCA of Ni, V and Zn distributions which identified two factors comprising the majority of distribution variance. This was spatially accounted for firstly by basalt rock types, with the second component associated with sandstone and limestone in the region. The results suggest trace element bioaccessibility and distribution is controlled by chemical and geologic processes which occur over variable spatial ranges of influence.

Using a Systematic Approach To Develop a Chemistry Course Introducing Students to Instrumental Analysis

A systematic approach to develop the teaching of instrumental analytical chemistry is discussed, as well as a conceptual framework for organizing and executing lectures and a laboratory course. Three main components are used in this course: theoretical knowledge developed in the classroom, simulations via a virtual laboratory, and practical training via experimentation. Problem-based learning and cooperative-learning methods are applied in both the classroom and laboratory aspects of the course. In addition, some reflections and best practices are presented on how to encourage students to learn actively. Overall, a student-centered environment is proposed that aims to cultivate students' practical abilities and individual talents.

Tracking the Fate of Microbially Sequestered Carbon Dioxide in Soil Organic Matter

The microbial contribution to soil organic matter (SOM) has recently been shown to be much larger than previously thought and thus its role in carbon sequestration may also be underestimated. In this study we employ C-13 ((CO2)-C-13) to assess the potential CO2 sequestration capacity of soil chemoautotrophic bacteria and combine nuclear magnetic resonance (NMR) with stable isotope probing (SIP), techniques that independently make use of the isotopic enrichment of soil microbial biomass. In this way molecular information generated from NMR is linked with identification of microbes responsible for carbon capture. A mathematical model is developed to determine real-time CO2 flux so that net sequestration can be calculated. Twenty-eight groups of bacteria showing close homologies with existing species were identified. Surprisingly, Ralstonia eutropha was the dominant group. Through NMR we observed the formation of lipids, carbohydrates, and proteins produced directly from CO2 utilized by microbial biomass. The component of SOM directly associated with CO2 capture was calculated at 2.86 mg C (89.21 mg kg(-1)) after 48 h. This approach can,differentiate between SOM derived through microbial uptake of CO2 and other SOM constituents and represents a first step in tracking the fate and dynamics of microbial biomass in soil.

Carbon nanotube modified carbon composite monoliths as superior adsorbents for carbon dioxide capture

Carbon composite monoliths were prepared from a commercial phenolic resin mixed with just 1 wt% of carbon nanotubes (CNTs) followed by carbonization and physical activation with CO. The products possess a hierarchical macroporous-microporous structure and superior CO adsorption properties. In particular, they show the top-ranked CO capacity (52 mg CO per g adsorbent at 25 °C and 114 mmHg) under low CO partial pressures, which is of more relevance for flue gas applications. This matches or exceeds those of carbons produced by complex chemical activation and functionalization. Our study demonstrates an effective way to create narrow micropores through structural modification of carbon composites by CNTs. © 2013 The Royal Society of Chemistry.

Rapid and nondestructive measurement of labile Mn, Cu, Zn, Pb and As in DGT by using field portable-XRF

The technique of diffusive gradients in thin films (DGT) is often employed to quantify labile metals in situ; however, it is a challenge to perform the measurements in-field. This study evaluated the capability of field-portable X-ray fluorescence (FP-XRF) to swiftly generate elemental speciation information with DGT. Biologically available metal ions in environmental samples passively preconcentrate in the thin films of DGT devices, providing an ideal and uniform matrix for XRF nondestructive detection. Strong correlation coefficients (r > 0.992 for Mn, Cu, Zn, Pb and As) were obtained for all elements during calibration. The limits of quantitation (LOQ) for the investigated elements of FP-XRF on DGT devices are 2.74 for Mn, 4.89 for Cu, 2.89 for Zn, 2.55 for Pb, and 0.48 for As (unit: µg cm(-2)). When Pb and As co-existed in the solution trials, As did not interfere with Pb detection when using Chelex-DGT. However, there was a significant enhancement of the Pb reading attributed to As when ferrihydrite binding gels were tested, consistent with Fe-oxyhydroxide surfaces absorbing large quantities of As. This study demonstrates the value of the FP-XRF technique to rapidly and nondestructively detect the metals accumulated in DGT devices, providing a new and simple diagnostic tool for on-site environmental monitoring of labile metals/metalloids

An evaluation of the capability of a biolayer interferometry biosensor to detect low-molecular-weight food contaminants

The safety of our food is an essential requirement of society. One well-recognised threat is that of chemical contamination of our food, where low-molecular-weight compounds such as biotoxins, drug residues and pesticides are present. Low-cost, rapid screening procedures are sought to discriminate the suspect samples from the population, thus selecting only these to be forwarded for confirmatory analysis. Many biosensor assays have been developed as screening tools in food contaminant analysis, but these tend to be electrochemical, fluorescence or surface plasmon resonance based. An alternative approach is the use of biolayer interferometry, which has become established in drug discovery and life science studies but is only now emerging as a potential tool in the analysis of food contaminants. A biolayer interferometry biosensor was assessed using domoic acid as a model compound. Instrument repeatability was tested by simultaneously producing six calibration curves showing replicate repeatability (n = 2) ranging from 0.1 to 6.5 % CV with individual concentration measurements (n = 12) ranging from 4.3 to 9.3 % CV, giving a calibration curve midpoint of 7.5 ng/ml (2.3 % CV (n = 6)). Reproducibility was assessed by producing three calibration curves on different days, giving a midpoint of 7.5 ng/ml (3.4 %CV (n = 3)). It was further shown, using assay development techniques, that the calibration curve midpoint could be adjusted from 10.4 to 1.9 ng/ml by varying assay parameters before the simultaneous construction of three calibration curves in matrix and buffer. Sensitivity of the assay compared favourably with previously published biosensor data for domoic acid. © 2013 Springer-Verlag Berlin Heidelberg.

Comparison of sample preparation methods, validation of an UPLC-MS/MS procedure for the quantification of tetrodotoxin present in marine gastropods and analysis of pufferfish

Tetrodotoxin (TTX) is one of the most potent marine neurotoxins reported. The global distribution of this toxin is spreading with the European Atlantic coastline now being affected. Climate change and increasing pollution have been suggested as underlying causes for this. In the present study, two different sample preparation techniques were used to extract TTX from Trumpet shells and pufferfish samples. Both extraction procedures (accelerated solvent extraction (ASE) and a simple solvent extraction) were shown to provide good recoveries (80-92%). A UPLC-MS/MS method was developed for the analysis of TTX and validated following the guidelines contained in the Commission Decision 2002/657/EC for chemical contaminant analysis. The performance of this procedure was demonstrated to be fit for purpose. This study is the first report on the use of ASE as a mean for TTX extraction, the use of UPLC-MS/MS for TTX analysis, and the validation of this method for TTX in gastropods.

Contemporary environmental issues of landfill leachate: assessment & remedies

Landfills are the primary option for waste disposal all over the world. Most of the landfill sites across the world are old and are not engineered to prevent contamination of the underlying soil and groundwater by the toxic leachate. The pollutants from landfill leachate have accumulative and detrimental effect on the ecology and food chains leading to carcinogenic effects, acute toxicity and genotoxicity among human beings. Management of this highly toxic leachate presents a challenging problem to the regulatory authorities who have set specific regulations regarding maximum limits of contaminants in treated leachate prior to disposal into the environment to ensure minimal environmental impact. There are different stages of leachate management such as monitoring of its formation and flow into the environment, identification of hazards associated with it and its treatment prior to disposal into the environment. This review focuses on: (i) leachate composition, (ii) Plume migration, (iii) Contaminant fate, (iv) Leachate plume monitoring techniques, (v) Risk assessment techniques, Hazard rating methods, mathematical modeling, and (vi) Recent innovations in leachate treatment technologies. However, due to seasonal fluctuations in leachate composition, flow rate and leachate volume, the management approaches cannot be stereotyped. Every scenario is unique and the strategy will vary accordingly. This paper lays out the choices for making an educated guess leading to the best management option.

Critical role of water in the direct oxidation of CO and hydrocarbons in diesel exhaust after treatment catalysis

CO and C3H6 oxidation have been carried out in the absence and presence of water over a Pd/Al2O3catalyst. It is clear that water promotes CO and, as a consequence, C3H6oxidation takes place at muchlower temperatures compared with the dry feed. The significant increase in the catalyst’s activity withrespect to CO oxidation is not simply associated with changes in surface concentration as a result ofcompetitive adsorption effects. Utilising18O2as the reactant allows the pathways whereby the oxidationdue to gaseous dioxygen and where the water activates the CO and C3H6to be distinguished. In thepresence of water, the predominant pathway is via water activation with C16O2and C16O18O being themajor species formed and oxidation with dioxygen plays a secondary role. The importance of wateractivation is further supported by the significant decrease in its effect when using D2O versus H2O.

Estrogenic endocrine disruptors present in sports supplements. A risk assessment for human health

Sports supplements are becoming a regular dietary addition for consumers who view such products as a means of improving their health and performance. Previously estrogenic endocrine disruptors (EDs) were detected in 80% of 116 sports supplements investigated by biological in vitro reporter gene assays (RGAs). The aim of this study was to quantify the hormonal activity in 50 of these sports supplement samples using a validated estrogen RGA and perform an exposure and risk assessment for human health. Results showed that 17β-estradiol equivalent levels were higher than those reported as being present in the typical human omnivore diet in 33 of the sports supplements and higher than the acceptable daily intake (ADI) in 13 of these products. The highest activity samples presented a potential to influence the human daily exposure to 17β-estradiol like activity in various risk groups with a predicted hormonal impact of greatest concern in young boys and postmenopausal women. In conclusion, consumers of sports supplements may be exposed to high levels of estrogenic EDs.

Chromatography- High Performance Liquid Chromatography

High-performance liquid chromatography (HPLC) is a major analytic tool in contemporary science, with possibly the highest number of systems installed and running globally. Modern HPLC offers high resolutions allowing the quantitative determination of target analytes within complex matrices by its compatibility with a number of detectors. The article describes the major technological characteristics of HPLC, reviewing separation mechanisms and their application in health and food science. Separation modes and media, key instrumental parameters, compatibility with detection modes, and applications are briefly discussed, aiming to provide helpful hints to the reader in the search for appropriate analytic techniques for a given task.

Multi-detection method for five common microalgal toxins based on the use of microspheres coupled to a flow-cytometry system

Freshwater and brackish microalgal toxins, such as microcystins, cylindrospermopsins, paralytic toxins, anatoxins or other neurotoxins are produced during the overgrowth of certain phytoplankton and benthic cyanobacteria, which includes either prokaryotic or eukaryotic microalgae. Although, further studies are necessary to define the biological role of these toxins, at least some of them are known to be poisonous to humans and wildlife due to their occurrence in these aquatic systems. The World Health Organization (WHO) has established as provisional recommended limit 1 μg of microcystin-LR per liter of drinking water. In this work we present a microsphere-based multi-detection method for five classes of freshwater and brackish toxins: microcystin-LR (MC-LR), cylindrospermopsin (CYN), anatoxin-a (ANA-a), saxitoxin (STX) and domoic acid (DA). Five inhibition assays were developed using different binding proteins and microsphere classes coupled to a flow-cytometry Luminex system. Then, assays were combined in one method for the simultaneous detection of the toxins. The IC₅₀'s using this method were 1.9 ± 0.1 μg L⁻¹ MC-LR, 1.3 ± 0.1 μg L⁻¹ CYN, 61 ± 4 μg L⁻¹ ANA-a, 5.4 ± 0.4 μg L⁻¹ STX and 4.9 ± 0.9 μg L⁻¹ DA. Lyophilized cyanobacterial culture samples were extracted using a simple procedure and analyzed by the Luminex method and by UPLC–IT-TOF-MS. Similar quantification was obtained by both methods for all toxins except for ANA-a, whereby the estimated content was lower when using UPLC–IT-TOF-MS. Therefore, this newly developed multiplexed detection method provides a rapid, simple, semi-quantitative screening tool for the simultaneous detection of five environmentally important freshwater and brackish toxins, in buffer and cyanobacterial extracts.

Mineralogical Characteristics and Transformations during Long-Term Operation of a Zerovalent Iron Reactive Barrier

Design and operation of Fe⁰ permeable reactive barriers (PRBs) can be improved by understanding the long-term mineralogical transformations that occur within PRBs. Changes in mineral precipitates, cementation, and corrosion of Fe⁰ filings within an in situ pilot-scale PRB were examined after the first 30 months of operation and compared with results of a previous study of the PRB conducted 15 months earlier using X-ray diffraction and scanning electron microscopy employing energy dispersive X-ray and backscatter electron analyses. Iron (oxy)hydroxides, aragonite, and maghemite and/or magnetite occurred throughout the cores collected 30 mo after installation. Goethite, lepidocrocite, mackinawite, aragonite, calcite, and siderite were associated with oxidized and cemented areas, while green rusts were detected in more reduced zones. Basic differences from our last detailed investigation include (i) mackinawite crystallized from amorphous FeS, (ii) aragonite transformed into calcite, (iii) akaganeite transformed to goethite and lepidocrocite, (iv) iron (oxy)hydroxides and calcium and iron carbonate minerals increased, (v) cementation was greater in the more recent study, and (vi) oxidation, corrosion, and disintegration of Fe⁰ filings were greater, especially in cemented areas, in the more recent study. If the degree of corrosion and cementation that was observed from 15 to 30 mo after installation continues, certain portions of the PRB (i.e., up-gradient entrance of the ground water to the Fe⁰ section of the PRB) may last less than five more years, thus reducing the effectiveness of the PRB to mitigate contaminants.