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.     

Acetamiprid, carbendazim, diuron and thiamethoxam sorption in two Brazilian tropical soils

Sorption of acetamiprid ((E)-N1-[(6-chloro-3-pyridyl)methyl]-N2-cyano-N1-methylacetamidine), carbendazim (methyl benzimidazol-2-ylcarbamate), diuron (N-(3,4-dichlorophenyl)-N, N-dimethyl urea) and thiamethoxam (3-(2-chloro-thiazol-5-ylmethyl)-5-methyl-[1,3,5]oxadiazinan-4-ylidene-N-nitroamine) was evaluated in two Brazilian tropical soils, Oxisol and Entisol, from Primavera do Leste region, Mato Grosso State, Brazil. To describe the sorption process, batch experiments were carried out. Linear and Freundlich isotherm models were used to calculate the K(d) and K(f) coefficients from experimental data. The K(d) values were utilized to calculate the partition coefficient normalized to soil organic carbon (K(oc)). For the pesticides acetamiprid, carbendazim, diuron and thiamenthoxan the K(oc) (mL g(- 1)) values ranged in both soils from 98 - 3235, 1024 - 2644, 145 - 2631 and 104 - 2877, respectively. From the studied pesticides, only carbendazim presented correlation (r(2) = 0.82 and p < 0.01) with soil organic carbon (OC) content. Acetamiprid and thiamethoxam showed low sorption coefficients, representing a high risk of surface and ground water contamination.     

Earth stewardship: Shaping a sustainable future through interacting policy and norm shifts

Transformation toward a sustainable future requires an earth stewardship approach to shift society from its current goal of increasing material wealth to a vision of sustaining built, natural, human, and social capital—equitably distributed across society, within and among nations. Widespread concern about earth’s current trajectory and support for actions that would foster more sustainable pathways suggests potential social tipping points in public demand for an earth stewardship vision. Here, we draw on empirical studies and theory to show that movement toward a stewardship vision can be facilitated by changes in either policy incentives or social norms. Our novel contribution is to point out that both norms and incentives must change and can do so interactively. This can be facilitated through leverage points and complementarities across policy areas, based on values, system design, and agency. Potential catalysts include novel democratic institutions and engagement of non-governmental actors, such as businesses, civic leaders, and social movements as agents for redistribution of power. Because no single intervention will transform the world, a key challenge is to align actions to be synergistic, persistent, and scalable.     

Application of the probability-based Maryland Biological Stream Survey to the state’s assessment of water quality standards

The Clean Water Act presents a daunting task for states by requiring them to assess and restore all their waters. Traditional monitoring has led to two beliefs: (1) ad hoc sampling (i.e., non-random) is adequate if enough sites are sampled and (2) more intensive sampling (e.g., collecting more organisms) at each site is always better. We analyzed the 1,500 Maryland Biological Stream Survey (MBSS) random sites sampled in 2000–2004 to describe the variability of Index of Biotic Integrity (IBI) scores at the site, reach, and watershed scales. Average variability for fish and benthic IBI scores increased with increasing spatial scale, demonstrating that single site IBI scores are not representative at watershed scales and therefore at best 25% of a state’s stream length can be representatively sampled with non-random designs. We evaluated the effects on total taxa captured and IBI precision of sampling for twice as many benthic macroinvertebrates at 73 MBSS sites with replicate samples. When sampling costs were fixed, the precision of the IBI decreased as the number of sites had to be reduced by 15%. Only 1% more taxa were found overall when the 73 sites where combined. We concluded that (1) comprehensive assessment of a state’s waters should be done using probability-based sampling that allows the condition across all reaches to be inferred statistically and (2) additional site sampling effort should not be incorporated into state biomonitoring when it will reduce the number of sites sampled to the point where overall assessment precision is lower.     

Precipitation Modeling by Polyhedral RCMARS and Comparison with MARS and CMARS

Climate change is becoming an ever important issue due to the possibility that it may result in extreme weather events such as floods or droughts. Consequently, precipitation forecasting has similarly gained in significance as it is a useful tool in meeting the increasing need for the efficient management of water resources as well as in preventing disasters before they happen. In the literature, there are various statistical and computational methods used for this purpose, including linear and nonlinear regression, kriging, time series models, neural networks, and multivariate adaptive regression splines (MARS). Among them, MARS stands out as the better performing precipitation modeling method. In this article, we used a recently developed method called robust conic mars (RCMARS), based on MARS (also on CMARS), to forecast precipitation owing to its ability to model complex uncertain data. In CMARS, which was developed as a powerful alternative to MARS, the model complexity is penalized in the form of Tikhonov regularization and studied as a conic quadratic programming. In RCMARS, on the other hand, CMARS is refined further by including the existence of uncertainty in the future scenarios and robustifying it with a robust optimization technique. To evaluate the performance of the RCMARS method, it was applied to build a precipitation model constructed as an early warning system for the continental Central Anatolia Region of Turkey, where drought has been a recurrent phenomenon for the last few decades. Furthermore, the performance of the RCMARS precipitation model was also compared to that of MARS and CMARS. The results indicated that RCMARS builds more accurate, precise, and stable precipitation models compared to those of MARS and CMARS. In addition to these advantageous features of the RCMARS precipitation model, it also provided a good fit to the data. As a result, we propose its use in precipitation forecasting for the region studied.     

A New Mathematical Approach in Environmental and Life Sciences: Gene–Environment Networks and Their Dynamics

An important research area in life sciences is devoted to modeling, prediction, and dynamics of gene-expression patterns. As clearly understood in these days, this enterprise cannot become satisfactory without acknowledging the role of the environment. To a representation of past, present, and most likely future states, we also encounter measurement errors and uncertainties. This paper surveys and improves recent advances in understanding the foundations and interdisciplinary implications of the newly introduced gene–environment networks, and it integrates the important theme of carbon dioxide emission reduction into the networks and dynamics. We also introduce some operational and managerial issues of practical working and decision making, expressed in terms of sliding windows, quadrants (modules) of parametric effects, and navigating (controlling) between such effects and directing them. Given data from DNA microarray experiments and environmental records, we extract nonlinear ordinary differential equations that contain parameters that have to be determined. For this, we employ modern (Chebychevian) approximation and (generalized semi-infinite) optimization. After this is provided, time- discretized dynamical systems are studied. A combinatorial algorithm with polyhedra sequences allows to detect the region of parametric stability. Finally, we analyze the topological landscape of gene–environment networks with its structural (in)stability. By embedding as a module and investigating CO₂ emission control and figuring out game theoretical aspects, we conclude. This pioneering work is theoretically elaborated, practically devoted to health care, medicine, education, living conditions, and environmental protection, and it invites the readers to future research.      

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.     

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.     

Dredging impact on an urbanized Florida bayou: effects on benthos and algal-periphyton.

Environmental effects of dredging events have been uncommonly reported for shallow, residential estuaries characteristic of the Gulf of Mexico region. The objective of this study was to determine the impact of hydraulic dredging on an urbanized estuary. Physicochemical quality, benthic community composition, whole sediment toxicity, periphytic algal community composition and trace metal tissue quality were determined prior to and after dredging. The effects on surface water pH, dissolved oxygen, and temperature were negligible but photosynthetically active radiation was decreased at several stations. Dredging significantly reduced benthic diversity and density (P < 0.05). However, the sediments were not acutely toxic to the epibenthic, Americamysis bahia (formerly Mysidopsis bahia); survival averaged 93% (post-dredging) and to 98% (pre-dredging). There were several post-dredging taxonomic structural changes in the diatom-dominated, periphyton community but differences in mean density and three diversity indices were not significant. Trace metal concentration in periphyton after dredging were reduced from an average of 4-65% and significantly for mercury, zinc and chromium in several areas. It was concluded that the environmental impact of small-scale dredging events in urbanized near-coastal areas, based on the selected parameters, are likely to be localized and of short-term environmental consequence. The choice of the target biota, response parameters and chemical analysis are important considerations in the environmental impact assessment of these periodic episodic events.