Calcareous electrochemical precipitation,a new method to trap nickel in seawater

There are few efficient, rapid and cheap methods to remove toxic metals from contaminated waters. Here we hypothesised that cathodic protection, an existing method used to control the corrosion of metallic structures, may trap toxic metals. Indeed, in seawater, the application of a cathodic current on a metallic structure induces the precipitation of limestone (CaCO₃) and magnesium dihydroxyde (Mg(OH)₂), thus forming a calcareous deposit on the metal surface. We therefore presumed that such calcareous deposit may trap metals dissolved in waters. Actually calcareous deposit formation has never been studied in the presence of dissolved metallic contaminants such as nickel. Here we tested ionic nickel (Ni²⁺) precipitation in calcareous deposit with a galvanized steel electrode by spiking artificial seawater with a NiCl₂ salt during 7 days of applied current. We analysed deposit surface and cross section by µ-Raman spectroscopy and scanning electron microscopy (SEM) with X-ray microanalysis. Ni concentration in the deposit was quantified by inductively coupled plasma analysis, after deposit dissolution in 60% HNO₃. Results show that in 7 days up to 24% of nickel can be trapped in the calcareous deposit. Scanning electron microscopy reveals that Ni is trapped under a pure CaCO₃ layer of aragonite. Raman spectra show that nickel is incorporated as nickel dihydroxyde (Ni(OH)₂), as evidence by vibration bands at 446 and 510 cm^?1. Overall our findings disclose a new and efficient method, calcareous electrochemical precipitation, which has potential applications to remove toxic metals from contaminated waters.     

Flow and drag force around a free surface piercing cylinder for environmental applications

This paper investigates flows around a free surface piercing cylinder with Froude number F > 0.5 and Reynolds number around Re = 50,000. The aim of this work is to gain a better understanding of the flow behaviour in environmental systems such as fishways. The advances are based upon experimental and numerical results. Several flow discharges and slopes are tested to obtain both subcritical and supercritical flows. The drag force exerted on the cylinder is measured with the help of a torque gauge while the velocity field is obtained using particle velocimetry. For the numerical part, two URANS turbulence models are tested, the k-\(\omega\) SST and the RNG k-\(\varepsilon\) models using the OpenFOAM software suite for subcritical cases, and then compared with the corresponding experimental results. With fishways applications in mind, the changes in drag coefficient \(C_d\) versus Froude number and water depth are studied and experimental correlations proposed. We conclude that the most suitable URANS turbulence model for reproducing this kind of flow is the k-\(\omega\) SST model.     

Evaluation of alternative filter media for particulate matter emission testing of residential wood heating devices

The performance of Teflon-coated glass fiber filter media (Pallflex Emfab TX40) is evaluated for particulate matter (PM) sampling of residential wood heating devices in a dilution tunnel. Thirty samples of varying duration and PM loading and concentration were collected from an U.S. Environmental Protection Agency (EPA) Method 28 dilution tunnel using dual Method 5G sample trains with untreated glass fiber and Emfab filters. Filters were weighed soon after the end of sampling and again the next day after equilibration at 35% relative humidity (RH). PM concentrations from both types of filters agreed very well with 1-day equilibration, demonstrating that Emfab filters are appropriate for use in measuring PM from residential wood burning appliances in a dilution tunnel and have performance equal to or better than the glass fiber filter media. Agreement between filter media without equilibration was erratic, with PM from glass fiber filter samples varying from slightly less than the Emfab samples to as much as 2.8 times higher. Some of the glass fiber filters lost substantial mass with equilibration, with the highest percent loss at lower filter mass loadings. Mass loss for Emfab samples was a small percentage of the mass and very consistent across the range of mass loadings. Taken together, these results may indicate water uptake on the glass fiber media that is readily removed with 1-day equilibration at moderate RH conditions.

Implications: EPA regulations now allow the use of either glass fiber or Teflon filter media for wood appliance PM emission testing. Teflon filter media minimizes the potential for acid-gas PM artifacts on glass fiber filters; this is important as EPA moves toward the use of locally sourced cordwood for testing that may have higher sulfur content. This work demonstrates that the use of Teflon-coated glass fiber filters can give similar PM measurement results to glass fiber filters after 1 day of equilibration. With no equilibration, measured PM from glass fiber filters was usually higher than from Teflon-coated glass fiber filters.     

Physical Characterization and Pre-assessment of Recycled High-Density Polyethylene as 3D Printing Material

3D printing has received lots of attention due to its limitless potential and advantages in comparison to traditional manufacturing processes. This study focuses on the most popular type of home 3D printers, namely fused filament fabrication (FFF) printers, which use plastic filaments as the feedstock. The rather high material cost and large amount of plastic waste generated by FFF 3D printers have driven the need for plastic filaments produced from recycled plastic waste. This study evaluates, in terms of physical characterization, the feasibility of using recycled high-density polyethylene (HDPE), one of the most commonly used plastics, as the feedstock for 3D printers, in comparison with the common acrylonitrile butadiene styrene plastic pellets. In-house extrusion using recycled HDPE pellets and flakes is possible. The diameter consistency and extrusion rate results, along with other physical characterization results, including differential scanning calorimetry, thermogravimetric analysis, Fourier transform infrared spectroscopy, Raman spectroscopy, and water absorption, suggest that making filaments from recycled HDPE pellets is a viable option, as the obtained filament has favorable water rejection and comparable extrusion rate and thermal stability. Existing methods for overcoming the warping and adhesion problems in 3D printing with HDPE were also reviewed. In order to increase the market competitiveness of waste-derived filaments, optimization of the extrusion process, studies on the mechanical and aging properties, and development of a standard characterization methodology and database are crucial.     

Novel and innovative pyrolysis and gasification technologies for energy efficient and environmentally sound MSW disposal

Within the context of European Union (EU) energy policy and sustainibility in waste management, recent EU regulations demand energy efficient and environmentally sound disposal methods of Municipal Solid Waste (MSW). Currently, landfill with its many drawbacks is the preferred option in the EU and many other industrialised countries. Within the waste management hierarchy thermal disposal especially incineration is a viable and proven alternative. But, the dominating method, mass-burn grate incineration has drawbacks as well particularly hazardous emissions and harmful process residues. In recent years, pyrolysis and gasification technologies have emerged to address these issues and improve the energy output. To keep the many players in the field comprehensively informed and up-to-date, novel and innovative technology approaches emphasising European developments are reviewed.     

PCB Levels and Trends Within the Detroit River-Western Lake Erie Basin: A Historical Perspective of Ecosystem Monitoring

An international workshop held in the spring of 2002 convened a group of technical experts to address monitoring, modeling, and management of PCBs within the Detroit River-Western Lake Erie basin. Participants shared and discussed a diverse set of research data bases pertaining to PCB levels within the region, discussed observed changes within different components of the local ecosystem, and identified several primary issues impacting future PCB management strategies. Results presented at the workshop indicate dramatic reductions in PCB contamination levels have been observed in much of study area between the late 1970s and mid-1990s. Estimates of loadings attributable to water and atmospheric sources have generally declined, as have PCB concentrations in herring gull eggs, smelt and walleye. Nevertheless, additional improvements have not been observed during recent years and elevated contamination levels remain a concern within local hot spots, particularly in the lower Detroit River and Trenton Channel. A primary recommendation broadly supported by workshop participants is the need to maintain, support, and coordinate a comprehensive ecosystem monitoring program for the Detroit River-Western Lake Erie basin, one that incorporates both near-field and far-field monitoring elements. Such a program is crucial to provide necessary data in support of understanding ecosystem trends, calculating annual mass loadings to the system, assessing impacts of remediation actions, developing improved modeling frameworks, and formulating cost-effective management strategies for the future.     

Persistent organic pollutants in European background air: derivation of temporal and latitudinal trends

Data are presented for polynuclear aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), polybrominated diphenyls ethers (PBDEs) and selected organochlorine compounds (OCs) in passive air samplers (PAS) along a rural/remote latitudinal transect from southern UK to northern Norway during 2002-2004. This study is part of an ongoing campaign, using semi-permeable membrane devices (SPMDs) as PAS over two year intervals since 1994. Data for PCBs, selected OCs and PBDEs are compared with that from previous campaigns. Absolute sequestered amounts of selected PCB congeners have decreased in a first order fashion between 1994-2004, with an average atmospheric clearance rate of 4.1 +/- 0.6 years and continue to fractionate with latitude. HCB has also declined between 1998-2004, with a clearance rate of 6 +/- 2.4 years. Data on DDT and its breakdown products indicate little fresh release in Europe. Comparison of PBDEs in 2000-02 and 2002-04 indicates site differences, generally with increases at UK sites and decreases in Norway. BDE-28, 47 and 49 decreased with increasing latitude (p < 0.04), while the other congeners did not show any significant latitudinal dependence. Transect data are presented for PAHs the first time. Three- and 4-ringed compounds dominated the mixture present in the SPMD. The PAH composition of the SPMDs at site 3 was compared to the average composition taken by active sampling at the same site. SPMD performance for sampling PAHs leaves many uncertainties, but they can be successfully used to semiquantitatively detect PAHs in the atmosphere. Fluorene and phenanthrene increased with latitude (p > 0.05), while 1-methylphenanthere, fluoranthene, benzo[b]fluoranthene and indeno[123-cd]pyrene decreased. Results are discussed in terms of sources, long-range atmospheric transport, global fractionation and clearance processes.     

An FTIR investigation of isocyanate skin absorption using in vitro guinea pig skin

Isocyanates may cause contact dermatitis, sensitization and asthma. Dermal exposure to aliphatic and aromatic isocyanates can occur in various exposure settings. The fate of isocyanates on skin is an important unanswered question. Do they react and bind to the outer layer of skin or do they penetrate through the epidermis as unreacted compounds? Knowing the kinetics of these processes is important in developing dermal exposure sampling or decontamination strategies, as well as understanding potential health implications such exposure may have. In this paper the residence time of model isocyanates on hairless guinea pig skin was investigated in vitro using attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectrometry. Model isocyanates tested were octyl isocyanate, polymeric hexamethylene diisocyanate isocyanurate (pHDI), polymeric isophorone diisocyanate isocyanurate (pIPDI) and methylenediphenyl diisocyanate (MDI). Isocyanates in ethyl acetate (30 microL) were spiked directly on the skin to give 0.2-1.8 micromol NCO cm(-2) (NCO = -N=C=O), and absorbance of the isocyanate group and other chemical groups of the molecule were monitored over time. The ATR-FTIR findings showed that polymeric isocyanates pHDI and pIPDI may remain on the skin as unreacted species for many hours, with only 15-20% of the total isocyanate group disappearing in one hour, while smaller compounds octyl isocyanate and MDI rapidly disappear from the skin surface (80+% in 30 min). Isocyanates most likely leave the skin surface by diffusion predominantly, with minimal reaction with surface proteins. The significance of these findings and their implications for dermal exposure sampling and isocyanate skin decontamination are discussed.     

Investigation of sequential and enzymatic extraction of arsenic from drinking water distribution solids using ICP-MS

A sequential extraction approach was utilized to estimate the distribution of arsenite [As(iii)] and arsenate [As(v)] on iron oxide/hydroxide solids obtained from drinking water distribution systems. The arsenic (As) associated with these solids can be segregated into three operationally defined categories (exchangeable, amorphous and crystalline) according to the sequential extraction literature. The exchangeable As, for the six drinking water solids evaluated, was estimated using 10 mM MgCl(2) and 10 mM NaH(2)PO(4) and represented between 5-34% of the total As available from the solid. The amorphously bound As was estimated using 10 mM (NH(4))(2)C(2)O(4) and represented between 57-124% of the As available from the respective solid. Finally, the crystalline bound As was estimated using titanium citrate and this represented less than 1.5% of the As associated with the solids. A synthetic stomach/intestine extraction approach was also applied to the distribution solids. The stomach fluid was found to extract between 0.5-33.3 microg g(-1) As and 120-2,360 microg g(-1) iron (Fe). The As concentrations in the intestine fluid were between 0.02-0.04 microg g(-1) while the Fe concentration ranged from 0.06-0.7 microg g(-1) for the first six drinking water distribution solids. The elevated Fe levels associated with the stomach fluid were found to produce Fe based precipitates when the intestinal treatment was applied. Preliminary observations indicate that most of the aqueous Fe in the stomach fluid is ferric ion and the observed precipitate produced in the intestine fluid is consistent with the decreased solubility of ferric ion at the pH associated with the intestine.