Diastereoisomer- and enantiomer-specific determination of hexabromocyclododecane in fish oil for food and feed

Fish oils are one of the main sources of ω-3 fatty acids. However, they can present elevated levels of some lipophilic pollutants, such as hexabromocyclododecanes (HBCDs). Since data about HBCDs in fish oil samples are very limited, in this study, 25 samples of fish oil for feed and food have been analyzed. Total HBCDs, as well as, α-, β- and γ-diastereoisomers have been determined. Total HBCDs ranged from 0.09 to 26.8 ng g⁻¹, with higher concentrations in fish oil for feed (average value of 9.69 ng g⁻¹) than those for food (1.14 ng g⁻¹). Concentrations of α-HBCD (average value of 4.12 ng g⁻¹ in feed samples and 0.48 ng g⁻¹ in food samples) and γ-HBCD (5.05 and 0.43 ng g⁻¹ respectively) were higher than that of β-HBCD (0.52 and 0.19 ng g⁻¹ respectively) in most of the samples. However, none of them was predominant in the samples. Concentrations of HBCDs were compared to concentrations of other pollutants and correlation between dioxin and dioxin-like PCBs levels and HBCDs levels were observed. Intake of HBCDs was calculated for fish oil with human consumption purposes and it ranged from 0.08 to 5.38 ng HBCDs d⁻¹, which could contribute significantly to HBCDs total intake. Enantiomeric fractions were also determined. No clear enrichment was observed for γ-HBCD, while (−)-α-HBCD enrichment was detected in some samples.     

Exposure assessment of pesticides in a shallow groundwater of the Tagus vulnerable zone (Portugal): a multivariate statistical approach (JCA)

Purpose

To assess groundwater exposure to pesticides, in agricultural areas of ??Ribatejo?? region (Portugal), and the influence of some key factors in that exposure, field, laboratory and modelling studies were carried out.

Methods

The study was performed in maize, potato, sugar beet, tomato and vegetables agricultural areas, located in a shallow aquifer, with pesticides use and, in most cases, with irrigation practices. Pesticides used in the studied agricultural areas and having leaching potential were selected, being considered also other pesticides included in priority lists, defined in Europe. Evaluation of groundwater exposure to pesticides was carried out by successively: (1) groundwater sampling in seven campaigns over the period 2004?C2006; (2) pesticide analysis [including isolation and concentration from the groundwater samples and further determination by gas chromatography?Cmass spectrometry (GC?CMS) of 14 herbicides, four insecticides and two metabolites]; and (3) analysis and discussion of the results by applying joint correspondence analysis (JCA).

Results

From the 20 pesticides and metabolites selected for the study, 11 were found in groundwater. Pesticides and metabolites most frequently detected were atrazine, alachlor, metolachlor, desethylatrazine, ethofumesate, ??-endosulfan, metribuzine, lindane and ??-endosulfan. The results showed that groundwater exposure to pesticides is influenced by local factors??either environmental or agricultural, as precipitation, soil, geology, crops and irrigation practices. Spring and autumn were more associated with the detection of pesticides being more likely to observe mixtures of these compounds in a groundwater sample in these transition seasons.

Conclusions

This work evidences the importance of models, which evaluate pesticides environmental behaviour, namely their water contamination potential (as Mackay multicompartimental fugacity model) and, specially, groundwater contamination potential (as GUS and Bacci and Gaggi leaching indices), in pesticide selection. Moreover, it reveals the importance to adapt proper statistical methods according to level of left-censored data. Using JCA was still possible to establish relations between pesticides and their temporal trend in a case study where there were more than 80% of data censored. This study will contribute to the Tagus river basin management plan with information on the patterns of pesticide occurrence in the alluvial aquifer system.     

Bisphenol A migration from plastic materials: direct insight of ecotoxicity in Daphnia magna

Bisphenol A (BPA) is an endocrine disrupting chemical (EDC) whose migration from food packaging is recognized worldwide. However, the real overall food contamination and related consequences are yet largely unknown. Among humans, children’s exposure to BPA has been emphasized because of the immaturity of their biological systems. The main aim of this study was to assess the reproductive impact of BPA leached from commercially available plastic containers used or related to child nutrition, performing ecotoxicological tests using the biomonitoring species Daphnia magna. Acute and chronic tests, as well as single and multigenerational tests were done. Migration of BPA from several baby bottles and other plastic containers evaluated by GC-MS indicated that a broader range of foodstuff may be contaminated when packed in plastics. Ecotoxicological test results performed using defined concentrations of BPA were in agreement with literature, although a precocious maturity of daphnids was detected at 3.0 mg/L. Curiously, an increased reproductive output (neonates per female) was observed when daphnids were bred in the polycarbonate (PC) containers (145.1?±?4.3 % to 264.7?±?3.8 %), both in single as in multigenerational tests, in comparison with the negative control group (100.3?±?1.6 %). A strong correlated dose-dependent ecotoxicological effect was observed, providing evidence that BPA leached from plastic food packaging materials act as functional estrogen in vivo at very low concentrations. In contrast, neonate production by daphnids cultured in polypropylene and non-PC bottles was slightly but not significantly enhanced (92.5?±?2.0 % to 118.8?±?1.8 %). Multigenerational tests also revealed magnification of the adverse effects, not only on fecundity but also on mortality, which represents a worrying trend for organisms that are chronically exposed to xenoestrogens for many generations. Two plausible explanations for the observed results could be given: a non-monotonic dose–response relationship or a mixture toxicity effect.     

Cadmium and zinc in vegetation and litter of a voluntary woodland that has developed on contaminated sediment-derived soil

Vegetation that develops spontaneously on metal-contaminated soils presents an opportunity to evaluate both metal bioavailability and the risks posed to biota. The behavior of Cd and Zn in the species of a spontaneously developed woodland, colonizing a canal embankment, has been investigated. Nitric-acid-extractable metal concentrations in the sediment-derived substrate ranged between 5.0 to 376 mg kg(-1)dry wt. Cd and 83.0 to 784 mg kg(-1)dry wt. Zn. The woodland is dominated by Willow (Salix) species. Salix caprea selectively accumulated Cd in all stem tissues, in contrast to S. viminalis, which regulated tissue Cd content. Both species showed an effective regulation of tissue Zn. Cadmium uptake by S. caprea was correlated with differences in soil pH, while Zn uptake was not. There was no relationship between tissue metal concentrations and soil metal nitric acid-extractable concentrations. Other aspects of ecosystem function appeared unaffected by the elevated Cd flux in S. caprea; leaf litter organisms present represented all major groups and there was no accumulation of organic matter. The woodland represents a potentially sustainable option for remediating a low value site with difficult access that does not involve removal of the contaminated material to a landfill or making a permanent inert cover.     

Occupational risk identification using hand-held or laptop computers.

This paper describes the Work Environment Profile (WEP) program and its use in risk identification by computer. It is installed into a hand-held computer or a laptop to be used in risk identification during work site visits. A 5-category system is used to describe the identified risks in 7 groups, i.e., accidents, biological and physical hazards, ergonomic and psychosocial load, chemicals, and information technology hazards. Each group contains several qualifying factors. These 5 categories are colour-coded at this stage to aid with visualization. Risk identification produces visual summary images the interpretation of which is facilitated by colours. The WEP program is a tool for risk assessment which is easy to learn and to use both by experts and nonprofessionals. It is especially well adapted to be used both in small and in larger enterprises. Considerable time is saved as no paper notes are needed.     

Risk homeostasis theory, utility and accident loss in a simulated driving task

The suggestion that utility is logically necessary for behavioural adjustments to be made in response to changes in intrinsic risk is fundamental to risk homeostasis theory (RHT). However, the methodology used to investigate RHT — analysis of road traffic accidents — is ill-suited to the investigation of this assertion. The role of utility and intrinsic risk as possible determinants of behavioural compensation were therefore examined experimentally across 14 specific behaviours using the Aston Driving Simulator. RHT predicts that these two factors act in a multiplicative way to form a statistical interaction. It also predicts that the behavioural pathways through which the effect manifests itself should be reconcilable with the concept of utility. Both predictions received little support in this experiment, suggesting that utility and intrinsic risk operate as independent factors: both factors produced significant main effects across a number of behaviours. This finding, if it can be generalised, implies that, contrary to mathematically-based models of danger compensation and the traditional model of risk homeostasis, utility is not logically necessary for behavioural compensation in response to a change in intrinsic risk.     

Method for determining minimum pool requirements to maintain and enhance salmonid fisheries in small Wyoming reservoirs

Methods for determination of minimum pool levels in reservoirs that consider sport fishery values are being sought by managers. We developed a technique for assessing the effects of incremental changes in minimum pool levels on potential salmonid abundance in small (<100 surface hectares at full pool) reservoirs in Wyoming managed for irrigation and municipal water supplies. The method has two components. One component is used to determine the minimum pool level needed to eliminate the risk of overwinter loss of salmonids due to low dissolved oxygen concentrations. The other component predicts the potential biomass of salmonids in reservoirs as a function of water depth and total dissolved solids concentration of the reservoir water. Application of the method is demonstrated for two reservoirs in Wyoming. The unit is jointly supported by the University of Wyoming, the Wyoming Game and Fish Department, and the US Fish and Wildlife Service.     

Use of sequential extraction to assess the influence of sewage sludge amendment on metal mobility in Chilean soils

In Chile, the increasing number of plants for the treatment of wastewater has brought about an increase in the generation of sludge. One way of sludge disposal is its application on land; this, however involves some problems, some of them being heavy metal accumulation and the increase in organic matter and other components from sewage sludge which may change the distribution and mobility of heavy metals. The purpose of the present study was to determine the effect of sewage sludge application on the distribution of Cr, Ni, Cu, Zn and Pb in agricultural soils in Chile. Three different soils, two Mollisols and one Alfisol, were sampled from an agricultural area in Central Chile. The soils were treated with sewage sludge at the rates of 0 and 30 ton ha(-1), and were incubated at 25 degrees C for 45 days. Before and after incubation, the soils were sequentially extracted to obtain labile (exchangeable and sodium acetate-soluble), potentially labile (soluble in moderately reducing conditions, K4P2O7-soluble and soluble in reducing conditions) and inert (soluble in strong acid oxidizing conditions) fractions. A two-level factored design was used to assess the effect of sludge application rate, incubation time and their interaction on the mobility of the elements under study. Among the metals determined in the sludge, zinc has the highest concentration. However, with the exception of Ni, the total content of metals was lower than the recommended limit values in sewage sludge as stated by Chilean regulations. Although 23% of zinc in sludge was in more mobile forms, the residual fraction of all metals was the predominant form in soils and sludge. The content of zinc only was significantly increased in two of the soils by sewage sludge application. On the other hand, with the exception of copper, the metals were redistributed in the first four fractions of amended soils. The effect of sludge application rate, incubation time and their interaction depended on the metal or soil type. In most cases an increase in more mobile forms of metals in soils was observed as the final effect.