Principles and application of an in vivo swine assay for the determination of arsenic bioavailability in contaminated matrices

The assessment of arsenic (As) bioavailability from contaminated matrices is a crucial parameter for reducing the uncertainty when estimating exposure for human health risk assessment. In vivo assessment of As utilising swine is considered an appropriate model for human health risk assessment applications as swine are remarkably similar to humans in terms of physiology and As metabolism. While limited in vivo As bioavailability data is available in the literature, few details have been provided regarding technical considerations for performing in vivo assays. This paper describes, with examples, surgical, experimental design and analytical issues associated with performing chronic and acute in vivo swine assays to determine As bioavailability in contaminated soil and food.     

Ethyl carbamate in foods and beverages: a review

Food and beverages contain many toxic chemicals that raise health concerns. Ethyl carbamate (EC) or urethane is the ethyl ester of carbamic acid. It occurs at low level, from ng/L to mg/L, in many fermented foods and beverages. Ethyl carbamate is genotoxic and carcinogenic for a number of species such as mice, rats, hamsters and monkeys. It has been classified as a group 2A carcinogen, “probably carcinogenic to humans”, by the World Health Organization’s International Agency for Research on Cancer (IARC) in 2007. The benchmark dose lower limit of ethyl carbamate is 0.3 mg/kg bw per day and the mean intake of ethyl carbamate from food is approximately 15 ng/kg bw per day. Those levels were calculated for relevant foods including bread, fermented milk products and soy sauce. Alcoholic beverages were not included in this calculation. However, high levels of ethyl carbamate can be found in distillated spirits at concentrations ranging from 0.01 to 12 mg/L depending on to the origin of spirit. Alcoholic drinks should thus be considered as a source of ethyl carbamate. Ethyl carbamate is produced by several chemical mechanisms: first, from urea and various proteins like citrulline produced during the fermentation step and second from cyanide, and hydrocyanic acid, via ethyl carbamate precursors such as cyanate. A large panel of ethyl carbamate formation mechanisms is described from simple ethanolysis of urea in homogeneous liquid phase to photochemical oxidation of cyanide ion or complex heterogeneous gas/solid catalytic reactions. Determination of ethyl carbamate in foods and beverages involves various strategies according to the material, food or beverage, solid or liquid, and according to the concentration, from ng/L to mg/L. Usually, adapted extractive techniques and pre-concentration step are followed by analysis by gas chromatography coupled to mass spectrometry (GC–MS of GC–MS–MS). High performance liquid chromatography (HPLC) and semi-quantitative spectroscopic methods (infra-red) are also proposed as valuable alternatives to the classical but time-consuming GC–MS. Various preventing methods are developed and used in some cases at industrial scale to lower ethyl carbamate levels in food. Two types of preventing methods are described. First, adapted and optimised practices in all step of the chain of foods’ (or beverages) production lead in general to low ethyl carbamate level. Second, the abatement of ethyl carbamate precursors can be done by adapted enzymatic, physical chemical or chemical methods according to the natures of raw materials and conditions of their production processes.     

On dispersion above a forest—Measurements and methods

Data collected over a mixed conifer/deciduous forest at the U.S. Department of Energy’s Savannah River Site in South Carolina using sonic anemometry reveal that on-site and real-time measurements of the velocity component standard deviations, σ_v and σ_w, are preferred for dispersion modeling. Such data are now easily accessible, from the outputs of cost-effective and rugged sonic anemometers. The data streams from these devices allow improvements to conventional methodologies for dispersion modeling. In particular, extrapolation of basic input data from a nearby location to the site of the actual release can be facilitated. In this regard reliance on the velocity statistics σ_v and σ_w appears to be preferred to the conventional σ_θ and σ_?. In the forest situations addressed here, the uncertainties introduced by extrapolating initializing properties (u, θ, σ_θ, and σ_?, or alternatively, σ_v and σ_w) from some location of actual measurement to some nearby location where an actual release occurs are similar to those associated with the spread of the plume itself and must be considered in any prediction of the likelihood of downwind concentration (exposure) exceeding some critical value, i.e., a regulatory standard. Consideration of plume expansion factors related to meander will not necessarily cause predicted downwind maxima within a particular plume to be decreased; however, the probability of exposure to this maximum value at any particular location will be reduced. Three-component sonic anemometers are affordable and reliable, and are now becoming a standard for meteorological monitoring programs subject to regulatory oversight. The time has come for regulatory agencies and the applied dispersion community to replace the traditional discrete sets of dispersion coefficients based on Pasquill stability by the direct input of measured turbulence data.

Implications: The continued endorsement of legacy Pasquill-Gifford stability schemes is presently under discussion among professional groups and regulatory agencies. The present paper is an attempt to introduce some rationality, for the case of a forested environment.     

Leaching of seven pesticides currently used in cotton crop in Mato Grosso State—Brazil

This study aimed to evaluate the leaching of pesticides and the applicability of the Attenuation Factor (AF) Model to predict their leaching. The leaching of carbofuran, carbendazim, diuron, metolachlor, α and β endosulfan and chlorpyrifos was studied in an Oxisol using a field experiment lysimeter located in Dom Aquino – Mato Grosso. The samples of percolated water were collected by rain event and analyzed. Chemical and physical soil attributes were determined before pesticide application to the plots. The results showed that carbofuran was the pesticide that presented a higher leaching rate in the studied soil, so was the one representing the highest contamination potential. From the total carbofuran applied in the soil surface, around 6 % leached below 50 cm. The other pesticides showed lower mobility in the studied soil. The calculated values to AF were 7.06E-12 (carbendazim), 5.08E-03 (carbofuran), 3.12E-17 (diuron), 6.66E-345 (α-endosulfan), 1.47E-162 (β-endosulfan), 1.50E-06 (metolachlor), 3.51E-155 (chlorpyrifos). AF Model was useful to classify the pesticides' potential for contamination; however, that model underestimated pesticide leaching.     

Recommendations on chemicals management policy and legislation in the framework of the Egyptian–German twinning project on hazardous substances and waste management

The sustainable management of chemicals and their associated wastes—especially legacy stockpiles—is always challenging. Developing countries face particular difficulties as they often have insufficient treatment and disposal capacity, have limited resources and many lack an appropriate and effective regulatory framework. This paper describes the objectives and the approach of the Egyptian–German Twinning Project under the European Neighbourhood Policy to improve the strategy of managing hazardous substances in the Egyptian Environmental Affairs Agency (EEAA) between November 2008 and May 2011. It also provides an introduction to the Republic of Egypt’s legal and administrative system regarding chemical controls. Subsequently, options for a new chemical management strategy consistent with the recommendations of the United Nations Chemicals Conventions are proposed. The Egyptian legal and administrative system is discussed in relation to the United Nations’ recommendations and current European Union legislation for the sound management of chemicals. We also discuss a strategy for the EEAA to use the existing Egyptian legal system to implement the United Nations’ Globally Harmonized System of Classification and Labelling of Chemicals, the Stockholm Convention and other proposed regulatory frameworks. The analysis, the results, and the recommendations presented may be useful for other developing countries in a comparable position to Egypt aspiring to update their legislation and administration to the international standards of sound management of chemicals.     

Assessment of five bioaccessibility assays for predicting the efficacy of petroleum hydrocarbon biodegradation in aged contaminated soils

In this study, the bioaccessibility of petroleum hydrocarbons in aged contaminated soils (1.6-67gkg(-1)) was assessed using four non-exhaustive extraction techniques (100% 1-butanol, 100% 1-propanol, 50% 1-propanol in water and hydroxypropyl-β-cyclodextrin) and the persulfate oxidation method. Using linear regression analysis, residual hydrocarbon concentrations following bioaccessibility assessment were compared to residual hydrocarbon concentrations following biodegradation in laboratory-scale microcosms in order to determine whether bioaccessibility assays can predict the endpoint of hydrocarbon biodegradation. The relationship between residual hydrocarbon concentrations following microcosm biodegradation and bioaccessibility assessment was linear (r(2)=0.71-0.97) indicating that bioaccessibility assays have the potential to predict the extent of hydrocarbon biodegradation. However, the slope of best fit varied depending on the hydrocarbon fractional range assessed. For the C(10)-C(14) hydrocarbon fraction, the slope of best fit ranged from 0.12 to 0.27 indicating that the non-exhaustive or persulfate oxidation methods removed 3.5-8 times more hydrocarbons than biodegradation. Conversely, for the higher molecular weight hydrocarbon fractions (C(29)-C(36) and C(37)-C(40)), biodegradation removed up to 3.3 times more hydrocarbons compared to bioaccessibility assays with the resulting slope of best fit ranging from 1.0-1.9 to 2.0-3.3 respectively. For mid-range hydrocarbons (C(15)-C(28)), a slope of approximately one was obtained indicating that C(15)-C(28) hydrocarbon removal by these bioaccessibility assays may approximate the extent of biodegradation. While this study demonstrates the potential of predicting biodegradation endpoints using bioaccessibility assays, limitations of the study include a small data set and that all soils were collected from a single site, presumably resulting from a single contamination source. Further evaluation and validation is required using soils from a range of hydrocarbon contamination sources in order to develop robust assays for predicting bioremediation endpoints in the field.     

Linking biomarkers to reproductive success of caged fathead minnows in streams with increasing urbanization

Reproductive and oxidative stress biomarkers have been recommended as tools to assess the health of aquatic organisms. Though validated in the laboratory, there are few studies that tie a change in gene expression to adverse reproductive or population outcomes in the field. This paper looked at 17 streams with varying degrees of urbanization to assess the use of biomarkers associated with reproduction or stress in predicting reproductive success of fathead minnows. In addition, the relationship between biomarkers and water quality measures in streams with varying degrees of urbanization was examined. Liver vitellogenin mRNA was correlated with reproduction within a period of 11 d prior to sampling irrespective of habitat, but its correlation with egg output declined at 12 d and beyond indicating its usefulness as a short-term biomarker but its limits as a biomarker of total reproductive output. Stress biomarkers such as glutathione S-transferase may be better correlated with factors affecting reproduction over a longer term. There was a significant correlation between GST mRNA and a variety of anthropogenic pollutants. There was also an inverse correlation between glutathione S-transferase and the amount of the watershed designated as wetland. Egg production over the 21-d was negatively correlated with the amount of urbanization and positively correlated to wetland habitats. This study supports the development of multiple biomarkers linking oxidative stress and other non-reproductive endpoints to changes in aquatic habitats will be useful for predicting the health of fish populations and identifying the environmental factors that may need mitigation for sustainable population management.     

Characterization of dioxin-like contamination in soil and sediments from the ��hot spot�� area of petrochemical plant in Pancevo (Serbia)

Purpose

Combinatorial bio/chemical approach was applied to investigate dioxin-like contamination of soil and sediment at the petrochemical and organochlorine plant in Pancevo, Serbia, after the destruction of manufacturing facilities that occurred in the spring of 1999 and subsequent remediation actions.

Materials and methods

Soil samples were analyzed for indicator polychlorinated biphenyls (PCBs) by gas chromatography/electron capture detection (GC/ECD). Prioritized soil sample and sediment samples from the waste water channel were analyzed for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) by high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS). Microethoxyresorufin o-deethylase (Micro-EROD) and H4IIE?Cluciferase bioassays were used for monitoring of dioxin-like compounds (DLC) and for better characterization of dioxin-like activity of soil samples.

Results

Bioanalytical results indicated high dioxin-like activity in one localized soil sample, while the chemical analysis confirmed the presence of large quantities of DLC: 3.0?×?10⁵ ng/g d.w. of seven-key PCBs, 8.2 ng/g d.w. of PCDD/Fs, and 3.0?×?10⁵ ng/g d.w. of planar and mono-ortho PCBs. In the sediment, contaminant concentrations were in the range 2?C8 ng/g d.w. of PCDD/Fs and 9?C20 ng/g d.w. of PCBs.

Conclusions

This study demonstrates the utility of combined application of bioassays and instrumental analysis, especially for developing and transition country which do not have capacity of the expensive instrumental analysis. The results indicate the high contamination of soil in the area of petrochemical plant, and PCDD/Fs contamination of the sediment from the waste water channel originating from the ethylene dichloride production.     

Matrix effects on the de novo synthesis of polychlorinated dibenzo-p-dioxins, dibenzofurans, biphenyls and benzenes

The formation of polychlorinated dibenzo-p-dioxins, dibenzofurans, biphenyls and benzenes in de novo synthesis experiments have been studied on model fly ashes with a wide range of matrices. The model fly ash consisted of 18 selected matrices with the addition of CuCl(2) x 2H(2)O, activated charcoal and NaCl. The studied matrices were not restricted to the commonly investigated matrices with defined chemical composition (silica gel, alumina, florisil) and industrially produced adsorbents with silicate structures (diatomaceous earths), but also included natural occurring matrices (clays, kaolin, bentonite and feldspars). In addition fly ashes from a hazardous waste incinerator were included in the study for comparison. Differences in the isomer composition (homologue profiles and isomer patterns) of the substances formed by de novo synthesis experiments are discussed in dependence on the chemical composition of the studied matrices. The de novo synthesis experiments on matrices with silicate structures resulted in high concentration of mainly perchlorinated aromatic compounds while for other matrices in particular alkaline matrices a homologue shift to lower chlorinated homologues and lower formation rates were found. The paper discusses the resulting PCDD/PCDF pattern and compares them to the PCDD/PCDF profile found in naturally occurring kaolin and ball clay (illite).     

Comparison of in vivo and in vitro methodologies for the assessment of arsenic bioavailability in contaminated soils

An in vivo swine assay was utilised for the determination of arsenic (As) bioavailability in contaminated soils. Arsenic bioavailability was assessed using pharmacokinetic analysis encompassing area under the blood plasma-As concentration time curve following zero correction and dose normalisation. In contaminated soil studies, As uptake into systemic circulation was compared to an arsenate oral dose and expressed as relative As bioavailability. Arsenic bioavailability ranged from 6.9+/-5.0% to 74.7+/-11.2% in 12 contaminated soils collected from former railway corridors, dip sites, mine sites and naturally elevated gossan soils. Arsenic bioavailability was generally low in the gossan soils and highest in the railway soils, ranging from 12.1+/-8.5% to 16.4+/-9.1% and 11.2+/-4.7% to 74.7+/-11.2%, respectively. Comparison of in vivo and in vitro (Simplified Bioaccessibility Extraction Test [SBET]) data from the 12 contaminated soils and bioavailability data collected from an As spiked soil study demonstrated that As bioavailability and As bioaccessibility were linearly correlated (in vivo As bioavailability (mgkg(-1))=14.19+0.93.SBET As bioaccessibility (mgkg(-1)); r(2)=0.92). The correlation between the two methods indicates that As bioavailability (in vivo) may be estimated using the less expensive, rapid in vitro chemical extraction method (SBET) to predict As exposure in human health risk assessment.