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.     

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.     

Characterizing the trophy hunting debate on Twitter

Social media is an arena of debate for contentious political and social topics. One conservation topic debated online is the acceptability of trophy hunting, a debate that has implications for national and international policy. We used a mixed-methods approach (grounded theory and quantitative clustering) to identify themes in the trophy hunting debate on Twitter. We examined commonly co-occurring categories that describe people's stances on trophy hunting. We identified 12 categories and 4 preliminary archetypes opposing trophy hunting—activism, scientific, condemning, and objecting—whose opposition derived from different moral reasoning. Few tweets (22) in our sample of 500 supported trophy hunting, whereas 350 opposed it. The debate was hostile; 7% of tweets in our sample were categorized as abusive. Online debates can be unproductive, and our findings may be important for stakeholders wishing to effectively engage in the trophy hunting debate on Twitter. More generally, we contend that because social media is increasingly influential, it is important to formally contextualize public responses to contentious conservation topics in order to aid communication of conservation evidence and to integrate diverse public perspectives in conservation practice.     

Monitoring OH-PCBs in PCB transport worker’s urine as a non-invasive exposure assessment tool

In this study, we analyzed hydroxylated polychlorinated biphenyls (OH-PCBs) in urine of both PCB transport workers and PCB researchers. A method to monitor OH-PCB in urine was developed. Urine was solid-phase extracted with 0.1% ammonia/ methanol (v/v) and glucuronic acid/sulfate conjugates and then decomposed using β-glucuronidase/arylsulfatase. After alkaline digestion/derivatization, the concentration of OH-PCBs was determined by HRGC/HRMS-SIM. In the first sampling campaign, the worker’s OH-PCB levels increased several fold after the PCB waste transportation work, indicating exposure to PCBs. The concentration of OH-PCBs in PCB transport workers’ urine (0.55~11 μg/g creatinine (Cre)) was higher than in PCB researchers’ urine (< 0.20 μg/g Cre). However, also a slight increase of OH-PCBs was observed in the researchers doing the air sampling at PCB storage area. In the second sampling, after recommended PCB exposure reduction measures had been enacted, the worker’s PCB levels did not increase during handling of PCB equipment. This suggests that applied safety measures improved the situation. Hydroxylated trichlorobiphenyls (OH-TrCBs) were identified as a major homolog of OH-PCBs in urine. Also, hydroxylated tetrachlorobiphenyls (OH-TeCBs) to hydroxylated hexachlorobiphenyls (OH-HxCBs) were detected. For the sum of ten selected major indicators, a strong correlation to total OH-PCBs were found and these can possibly be used as non-invasive biomarkers of PCB exposure in workers managing PCB capacitors and transformer oils. We suggest that monitoring of OH-PCBs in PCB management projects could be considered a non-invasive way to detect exposure. It could also be used as a tool to assess and improve PCB management. This is highly relevant considering the fact that in the next 10 years, approx. 14 million tons of PCB waste need to be managed. Also, the selected populations could be screened to assess whether exposure at work, school, or home has taken place.     

Advances and perspective in bioremediation of polychlorinated biphenyl-contaminated soils

In recent years, microbial degradation and bioremediation approaches of polychlorinated biphenyls (PCBs) have been studied extensively considering their toxicity, carcinogenicity and persistency potential in the environment. In this direction, different catabolic enzymes have been identified and reported for biodegradation of different PCB congeners along with optimization of biological processes. A genome analysis of PCB-degrading bacteria has led in an improved understanding of their metabolic potential and adaptation to stressful conditions. However, many stones in this area are left unturned. For example, the role and diversity of uncultivable microbes in PCB degradation are still not fully understood. Improved knowledge and understanding on this front will open up new avenues for improved bioremediation technologies which will bring economic, environmental and societal benefits. This article highlights on recent advances in bioremediation of PCBs in soil. It is demonstrated that bioremediation is the most effective and innovative technology which includes biostimulation, bioaugmentation, phytoremediation and rhizoremediation and acts as a model solution for pollution abatement. More recently, transgenic plants and genetically modified microorganisms have proved to be revolutionary in the bioremediation of PCBs. Additionally, other important aspects such as pretreatment using chemical/physical agents for enhanced biodegradation are also addressed. Efforts have been made to identify challenges, research gaps and necessary approaches which in future, can be harnessed for successful use of bioremediation under field conditions. Emphases have been given on the quality/efficiency of bioremediation technology and its related cost which determines its ultimate acceptability.     

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.