Mathematical analysis of the whole core injection method accuracy for measuring phenanthrene biodegradation rates in undisturbed marine sediments

Rates of 14C-phenanthrene mineralization in contaminated, undisturbed marine sediments were measured using the whole core injection method to assess microbial natural attenuation activity as a function of sediment depth. Submerged sediments were sampled from Eagle Harbor, a marine superfund site in Puget Sound. Experiments show significant biodegradation activities (0.0012-0.0036 day(-1)) in the sediment horizons from 0 to 10 cm. The purpose and scope of this paper is to evaluate the range of experimental conditions giving valid results; a mathematical simulation described competing contaminant 14C-phenanthrene diffusion and simultaneous biodegradation (Monod kinetics), both retarded by sorption. The effect of aging was examined with two sorption models in presumed pseudo-homogenous sediments having effective properties. The simulation predictions provide quantitative guidelines for the successful use of the whole core injection method. (1) The effective Monod constant KS' in sediment is increased by a large partition coefficient KP between sediment and water and makes the apparent 14C-phenanthrene biodegradation approach first-order kinetics. (2) When KS'>1 mg(-1) l(-1), the measured 14C-phenanthrene biodegradation extent is biased by inadequately distributed injected tracer only when less than 7% of the sediment horizon is initially probed and mixed with injected tracer. (3) A short incubation time (<20 days) is necessary when a mobile indicator, e.g., gaseous 14CO2, is used. For longer incubation times, predictions show that a 14CO2 indicator diffuses to adjacent horizons, thus smearing the depth profile of biodegradation. (4) This method employing a radiolabeled tracer provides accurate biodegradation rates for freshly contaminated sediments, and represents an upper limit to the natural phenanthrene biodegradation extents if the contaminant is aged over 50 days.     

Optimisation of pressurised liquid extraction for elimination of sulphur interferences during determination of organotin compounds in sulphur-rich sediments by gas chromatography with flame photometric detection

A simple method for species-selective analysis of organotin compounds (OTCs) (butyl and phenyl) in sediments was developed. The sample preparation procedure was specifically optimised for sulphur-rich sediments to eliminate interferences from elemental sulphur and organosulphur compounds. Tin species were extracted from sediment samples using pressurised liquid extraction technique (PLE), ethylated - with simultaneous extraction to isooctane - in aqueous phase with sodium tetraethylborate (NaBEt(4)) and separated/detected by gas chromatography with flame photometric detection (GC-FPD). PLE operational variables (extraction temperature and pressure, solvent composition and number of static extraction steps) and extract handling routine were fine-tuned to minimise the amount of extracted interferents while keeping OTCs recovery at an acceptable level. Best results were obtained after extraction of sediment samples with methanol/water (75% v/v methanol) solution of acetic acid/sodium acetate with tropolone addition (0.6 g l(-1)). Derivatisation of low temperature, high-pressure (50 degrees C, 13.8 MPa) extracts gives isooctane extracts which are clean enough to be directly analysed by GC-FPD without any further cleanup. Interferences from elemental sulphur were completely eliminated while concentrations of other interferents were reduced to the level not impairing quantitation of OTCs under the study. No negative effects in terms of chromatographic column deterioration were observed after repeated injections of such extracts. Two certified reference materials, BCR646 and PACS-2, were analysed to assess performance of the method. Recoveries of all OTCs under the study, except MBT, were in the range of 91-114%. MBT extraction efficiency was low (34-47%) therefore the method is unsuitable for precise determinations of this compound.     

The use of NTA and EDDS for enhanced phytoextraction of metals from a multiply contaminated soil by Brassica carinata

The potential of nine different species to grow in the presence of metals (As, Cd, Cu, Pb and Zn) and to accumulate them in the shoots was assessed for each metal separately by germination and root length tests, and successively by hydroponic experiments. Of the nine species tested, Brassica carinata was the species that accumulated the highest amounts of metals in shoots without suffering a significant biomass reduction. To further evaluate the potential of B. carinata for chelant-enhanced phytoextraction of a natural, multiply metal-polluted soil (As, Cd, Cu, Pb and Zn), both hydroponic and pot experiments were carried out with nitrilotriacetic acid (NTA) or (S,S)-ethylenediamine disuccinic acid (EDDS) as complexing agents. The hydroponic study with solutions containing the five metals together showed that accumulation of Cd, Cu, Pb and Zn in shoots was higher following EDDS addition compared to NTA. EDDS was more effective than NTA in desorbing Cu, Pb and Zn from the soil, whereas As and Cd were poorly extracted. B. carinata plants were grown for 4 weeks in the multiply metal-contaminated soil and then the soil was amended with 5 mmol kg(-1) NTA or EDDS. All plants were harvested 1 week after amendment. In comparison to NTA, EDDS was more effective in enhancing the concentrations of Cu, Pb and Zn in B. carinata shoots (2- to 4-fold increase compared to the control). One week after chelant addition, the DTPA-extractable metal concentrations in the polluted soil were lower in the EDDS treatment in comparison with the NTA amendment. Even though B. carinata showed a reduced growth and a relatively low metal uptake, it demonstrated the ability to survive and tolerate the presence of more metals simultaneously.     

The contingent effect of constructive confrontation on the relationship between shared mental models and decision quality

Work teams are being utilized more frequently to give organizations access to the broader knowledge and skill base of employees, as well as to provide for adaptive, efficient decision‐making. In teams, we argue that constructive confrontation norms are an important contingency variable in the relationship between mental model similarity and decision quality. Mental model similarity helps team members understand one another's perspectives and reduces the likelihood of conflict. Accordingly, mental model similarity improves decision quality. When strong norms of constructive confrontation are in place, however, teams are in a better position to reap the benefits of conflict (greater diversity of inputs) without experiencing its negative consequences. Thus, when constructive confrontation norms are strong, less mental model similarity (i.e., more diversity of perspectives) is likely to improve decision quality. Copyright © 2007 John Wiley & Sons, Ltd.     

Polycyclic aromatic hydrocarbon levels in European catfish from the upper Po River basin

Polycyclic aromatic hydrocarbons (PAHs) are a major concern in environmental studies as many of them have been labeled as probable carcinogens by the International Agency for Research on Cancer (IARC 1983). Due to their lipophilic properties and resistance to degradation, PAHs can accumulate in organic tissue. As a consequence, alarming concentrations of these compounds have been found in many aquatic species. The European catfish (Silurus glanis) is a top food chain predator that is considered to be a reliable bio-indicator of environmental pollution. From 2009 to 2011, 54 specimens of S. glanis were captured from four different sites covering the area of the Po River basin (Northern Italy). Fish muscles were analyzed in the laboratory to determine the levels of nine PAHs, namely naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, pyrene, benz[a]anthracene, chrysene, and benz[a]pyrene (BaP), which were detected by high-performance liquid chromatography (HPLC). The total average concentration of PAHs was 26.90?±?49.50 ng g^?1 (min 0.60, max 275.75 ng g^?1). Analysis showed that 9.20 % of the fish muscles exceeded the maximum levels of 2 ng g^?1 set for BaP by European regulations (Commission Regulation (EC), 2006). Values measured for benz[a]pyrene ranged from 0.05 to 8.20 ng g^?1 (mean 1.07?±?1.58 ng g^?1). Chrysene and benz[a]anthracene, both considered potential human carcinogens (PAH2), were found at levels of 4.40 and 0.05 ng g^?1 (mean values), respectively. The highest mean concentration was recorded for anthracene (12.92 ng g^?1), which has been recently included in the list of substances of very high concern (SVHC) as reported by the European Chemicals Agency (ECHA 1–9, 2009).     

The New Bedford Harbor Superfund site long-term monitoring program (1993–2009)

New Bedford Harbor (NBH), located in southeastern Massachusetts, was designated as a marine Superfund site in 1983 due to sediment contamination by polychlorinated biphenyls (PCBs). Based on risks to human health and the environment, the first two phases of the site cleanup involved dredging PCB-contaminated sediments from the harbor. Therefore, a long-term monitoring program (LTM) was developed to measure spatial and temporal chemical and biological changes in sediment, water, and biota to assess the effects and effectiveness of the remedial activities. A systematic, probabilistic sampling design was used to select sediment sampling stations. This unbiased design allowed the three segments of the harbor to be compared spatially and temporally to quantify changes resulting from dredging the contaminated sediments. Sediment was collected at each station, and chemical (e.g., PCBs and metals), physical (e.g., grain size), and biological (e.g., benthic community) measurements were conducted on all samples. This paper describes the overall NBH-LTM approach and the results from the five rounds of sample collections. There is a decreasing spatial gradient in sediment PCB concentrations from the northern boundary (upper harbor) to the southern boundary (outer harbor) of the site. Along this same transect, there is an increase in biological condition (e.g., benthic community diversity). Temporally, the contaminant and biological gradients have been maintained since the 1993 baseline collection; however, since the onset of full-scale remediation, PCB concentrations have decreased throughout the site, and one of the benthic community indices has shown significant improvement in the lower and outer harbor areas.     

Environmental and biological monitoring of benzene in traffic policemen, police drivers and rural outdoor male workers

To evaluate exposure to benzene in urban and rural areas, an investigation into personal exposure to benzene in traffic policemen, police drivers and rural (roadmen) male outdoor workers was carried out. Personal samples and data acquired using fixed monitoring stations located in different areas of the city were used to measure personal exposure to benzene in 62 non-smoker traffic policemen, 22 police drivers and 57 roadmen. Blood benzene, urinary trans-trans muconic acid (t,t-MA) and S-phenyl-mercapturic acid (S-PMA) were measured at the end of work shift in 62 non-smoker traffic policemen, 22 police drivers and 57 roadmen and 34 smoker traffic policemen, 21 police drivers and 53 roadmen. Exposure to benzene was similar among non-smoker traffic policemen and police drivers and higher among non-smoker urban workers compared to rural workers. Blood benzene, t,t-MA and S-PMA were similar among non-smoker traffic policemen and police drivers; blood benzene and t,t-MA were significantly higher in non-smoker urban workers compared to rural workers. Significant increases in t,t-MA were found in smokers vs. non-smokers. In non-smoker urban workers airborne benzene and blood benzene, and t,t-MA and S-PMA were significantly correlated. This study gives an evaluation of the exposure to benzene in an urban area, comparing people working in the street or in cars, to people working in a rural area. Benzene is a certain carcinogen for humans. The results we showed should lead to more in-depth studies about the effects on health of these categories of workers.     

The levels and composition of persistent organic pollutants in alluvial agriculture soils affected by flooding

The concentrations and composition of persistent organic pollutants (POPs) were determined in alluvial soils subjected to heavy flooding in a rural region of Poland. Soil samples (n?=?30) were collected from the upper soil layer from a 70-km² area. Chemical determinations included basic physicochemical properties and the contents of polychlorinated biphenyls (PCBs), hexachlorocyclohexanes (HCHs), dichlorodiphenyltrichloroethanes (DDTs) and polycyclic aromatic hydrocarbons (PAHs, 16 compounds). The median concentrations of Σ7PCB (PCB28?+?PCB52?+?PCB101?+?PCB118?+?PCB138?+?PCB153?+?PCB180), Σ3HCH (α-HCH?+?β-HCH?+?γ-HCH) and Σ3pp′(DDT?+?DDE?+?DDD) were 1.60?±?1.03, 0.22?±?0.13 and 25.18?±?82.70 μg kg^?1, respectively. The median concentrations of the most abundant PAHs, phenanthrene, fluoranthene, pyrene, benzo[b]fluoranthene and benzo[a]pyrene were 50?±?37, 38?±?27, 29?±?30, 45?±?36 and 24?±?22 μg kg^?1, respectively. Compared with elsewhere in the world, the overall level of contamination with POPs was low and similar to the levels in agricultural soils from neighbouring countries, except for benzo[a]pyrene and DDT. There was no evidence that flooding affected the levels of POPs in the studied soils. The patterns observed for PAHs and PCBs indicate that atmospheric deposition is the most important long-term source of these contaminants. DDTs were the dominant organochlorine pesticides (up to 99 %), and the contribution of the parent pp′ isomer was up to 50 % of the ΣDDT, which indicates the advantage of aged contamination. A high pp′DDE/pp′DDD ratio suggests the prevalence of aerobic transformations of parent DDT. Dominance of the γ isomer in the HCHs implies historical use of lindane in the area. The effect of soil properties on the POP concentrations was rather weak, although statistically significant links with the content of the <0.02-mm fraction, C_total or N_total were observed for some individual compounds in the PCB group.     

Double Green Process: a low environmental impact method for recycling of CdTe,a-Si and CIS/CIGS thin-film photovoltaic modules

On the basis of the method for managing the end of life of CdTe photovoltaic panels previously proposed by the authors, a new method for the recycling of all types of thin-film panels (CdTe, a-Si and CIS/CIGS) has been developed and optimised under a research project founded by Enel Foundation and CRUI Foundation. The DGP process has been developed through a feasibility study carried out from three points of view: technical, environmental and economic. The process is composed by two sub-processes matched to each other, one suitable for CdTe panels (named DGPa) and the other one for a-Si and CIS/CIGS panels (DGPb). The Double Green Panel process is based mainly on mechanical treatments with a minimum use of chemicals and it is characterised by a greater level of automation and a high flexibility in production capacity. The potential environmental impacts of various configurations of the DGP process have been extensively analysed with LCA tool in order to develop an environmentally friendly process. The economic feasibility has been assessed through the Discounted Cash Flow Analysis (DCFA) method. The revenues associated to the recovery of valuable and common materials and the recycling costs have been taken into account.