Trevor Kletz,friend and mentor

I am very pleased to have this opportunity to present these thoughts on my personal relationship with Trevor Kletz and the impact he has had on my own career in the field of process safety.     

Copper distribution in surface and subsurface soil horizons

The horizons of four natural soils were treated with Cu²⁺ in an acid medium to study the retention capacity of Cu. The possible mineralogical changes arising because of the treatment were also studied. The soil properties and characteristics with the greatest influence on the metal retention and its distribution among the different soil fractions were determined. Crystalline phases of each horizon were determined by X-ray diffraction (XDR). The morphology, structural distribution and particle chemical composition of soil samples were investigated using field emission scanning electron microscopy. Cu distribution in the different geochemical phases of the soil was studied using a sequential extraction. The treatment led to an increase in the amorphous phases and the formation of new crystalline phases, such as rouaite (Cu₂(NO₃)(OH)₃) and nitratine (NaNO₃). Cu was also found superficially sorbed on amorphous hydroxy compounds of Fe that interact with albite, muscovite and gibbsite, and also on spherical and curved particles of aluminium clays. The largest amount of Cu retained was in an exchangeable form, and the smallest amount associated with the crystalline Fe oxides and residual fraction. In the surface horizons, the predominant Cu retention process is complexation in organomineral associations, while in the subsurface horizons it is adsorption.     

TiO₂-based nanoparticles released in water from commercialized sunscreens in a life-cycle perspective: structures and quantities

This work investigates the physical-chemical evolution during artificial aging in water of four commercialized sunscreens containing TiO₂-based nanocomposites. Sunscreens were analyzed in terms of mineralogy and TiO₂ concentration. The residues formed after aging were characterized in size, shape, chemistry and surface properties. The results showed that a significant fraction of nano-TiO₂ residues was released from all sunscreens, despite their heterogeneous behaviors. A stable dispersion of submicronic aggregates of nanoparticles was generated, representing up to 38 w/w% of the amount of sunscreen, and containing up to 30% of the total nano-TiO₂ initially present in the creams. The stability of the dispersion was tested as a function of salt concentration, revealing that in seawater conditions, a major part of these nano-TiO₂ residues will aggregate and sediment. These results were put in perspective with consumption and life cycle of sunscreens to estimate the amount of nano-TiO₂ potentially released into AQUATIC environment.     

Partitioning of metals in a degraded acid sulfate soil landscape: influence of tidal re-inundation

The oxidation and acidification of sulfidic soil materials results in the re-partitioning of metals, generally to more mobile forms. In this study, we examine the partitioning of Fe, Cr, Cu, Mn, Ni and Zn in the acidified surface soil (0-0.1 m) and the unoxidised sub-soil materials (1.3-1.5 m) of an acid sulfate soil landscape. Metal partitioning at this acidic site was then compared to an adjacent site that was previously acidified, but has since been remediated by tidal re-inundation. Differences in metal partitioning were determined using an optimised six-step sequential extraction procedure which targets the “labile”, “acid-soluble”, “organic”, “crystalline oxide”, “pyritic” and “residual” fractions. The surficial soil materials of the acidic site had experienced considerable losses of Cr, Cu, Mn and Ni compared to the underlying parent material due to oxidation and acidification, yet only minor losses of Fe and Zn. In general, the metals most depleted from the acidified surface soil materials exhibited the greatest sequestration in the surface soil materials of the tidally remediated site. An exception to this was iron, which accumulated to highly elevated concentrations in the surficial soil materials of the tidally remediated site. The “acid-soluble”, “organic” and “pyritic” fractions displayed the greatest increase in metals following tidal remediation. This study demonstrates that prolonged tidal re-inundation of severely acidified acid sulfate soil landscapes leads to the immobilisation of trace metals through the surficial accumulation of iron oxides, organic material and pyrite.     

Viable skin efficiently absorbs and metabolizes bisphenol A

Skin contact has been hypothesized to contribute to human exposure to bisphenol A (BPA). We examined the diffusion and metabolism of BPA using viable skin models: human skin explants and short-term cultures of pig ear skin, an alternative model for the study of the fate of xenobiotics following contact exposure. ¹⁴C-BPA [50-800 nmol] was applied on the surface of skin models. Radioactivity distribution was measured in all skin compartments and in the diffusion cells of static cells diffusion systems. BPA and metabolites were further quantified by radio-HPLC. BPA was efficiently absorbed in short-term cultures, with no major difference between the models used in the study [viable pig ear skin: 65%; viable human explants: 46%; non-viable (previously frozen) pig skin: 58%]. BPA was extensively metabolized in viable systems only. Major BPA metabolites produced by the skin were BPA mono-glucuronide and BPA mono-sulfate, accounting together for 73% and 27% of the dose, in pig and human, respectively. In conclusion, experiments with viable skin models unequivocally demonstrate that BPA is readily absorbed and metabolized by the skin. The trans-dermal route is expected to contribute substantially to BPA exposure in human, when direct contact with BPA (free monomer) occurs.     

Phenol depletion by thermally activated peroxydisulfate at 70°C

The ability of thermal activated peroxydisulfate (PS) of mineralizing phenol at 70 °C from contaminated waters is investigated. Phenol in concentrations of 10⁻⁴ to 5 × 10⁻⁴ M is quantitatively depleted by 5 × 10⁻³ to 10⁻² M activated PS in 15 min of reaction. However, mineralization of the organic carbon is not observed. Instead, an insoluble phenol polymer-type product is formed. A reaction mechanism including the formation of phenoxyl radicals and validated by computer simulations is proposed. High molecular weight phenolic products are formed by phenoxyl radical H-abstraction reactions. This is not the case for the room temperature degradation of phenol by sulfate radicals where sulfate addition to the aromatic ring mainly leads to the generation of hydroxycyclohexadienyl radicals leading to hydroxybenzenes and oxidized open chain products. Therefore, a change in the reaction mechanism is observed with increasing temperature, and thermal activation of PS at 70 °C does not lead to the mineralization of phenol. Thus PS activation at 70 °C may be considered a potential method to reduce the load of phenol in polluted waters by polymerization.     

Soil pH effects on the interactions between dissolved zinc,non-nano- and nano-ZnO with soil bacterial communities

Zinc oxide nanoparticles (ZnO NPs) are used in an array of products and processes, ranging from personal care products to antifouling paints, textiles, food additives, antibacterial agents and environmental remediation processes. Soils are an environment likely to be exposed to manmade nanoparticles due to the practice of applying sewage sludge as a fertiliser or as an organic soil improver. However, understanding on the interactions between soil properties, nanoparticles and the organisms that live within soil is lacking, especially with regards to soil bacterial communities. We studied the effects of nanoparticulate, non-nanoparticulate and ionic zinc (in the form of zinc chloride) on the composition of bacterial communities in soil with a modified pH range (from pH 4.5 to pH 7.2). We observed strong pH-dependent effects on the interaction between bacterial communities and all forms of zinc, with the largest changes in bacterial community composition occurring in soils with low and medium pH levels (pH 4.8 and 5.9). The high pH soil (pH 7.2) was less susceptible to the effects of zinc exposure. At the highest doses of zinc (2500 mg/kg dw soil), both nano and non-nano particulate zinc applications elicited a similar response in the soil bacterial community, and this differed significantly to the ionic zinc salt treatment. The results highlight the importance of considering soil pH in nanotoxicology studies, although further work is needed to determine the exact mechanisms controlling the toxicity and fate and interactions of nanoparticles with soil microbial communities.     

Air toxics in Canada measured by the National Air Pollution Surveillance (NAPS) program and their relation to ambient air quality guidelines

This study reports ambient concentrations of 63 air toxics that were measured in Canada by the National Air Pollution Surveillance (NAPS) program over the period 2009–2013. Measured concentrations are compared with ambient air quality guidelines from Canadian jurisdictions, and compounds that exceeded guidelines are identified and discussed. Although this study does not assess risk or cumulative effects, air toxics that approached guidelines are also identified so that their potential contribution to ambient air toxics pollution can be considered. Eleven air toxics exceeded at least one guideline, and an additional 16 approached guidelines during the study period. Four compounds were measured using methods whose detection limits exceeded a guideline value, three of which could not be compared with guidelines, since they were not detected in any samples. The assessment of several metal(loid) concentrations is tentative, since they were measured only in fine particulate matter (PM) but compared with guidelines based on coarse or total PM. Improvements to sampling and analysis techniques for the latter compounds as well as for those whose methods are subject to known uncertainties would improve confidence in reported concentrations and their relation to applicable guidelines. Analysis of sampling strategies for all compounds found to exceed or approach guidelines would contribute to ensuring that their spatiotemporal coverage is adequate. Examination of the air toxics not measured by NAPS but having guidelines in Canadian jurisdictions or being included in other programs such as the U.S. National-Scale Air Toxics Assessment (NATA) would contribute to ensuring that the full suite of pollutants relevant to ambient air quality in Canada is subject to adequate study. The results of this study can be applied to evaluating the effectiveness of toxic substances management in Canada.

Implications: Recent measurements of 63 air toxics in Canada by the National Air Pollution Surveillance (NAPS) program showed that 11 compounds exceeded daily or annual ambient air quality guidelines and that an additional 16 compounds approached such guidelines within an order of magnitude. The results of this study can be applied to evaluating the effectiveness of toxic substances management in Canada and to identifying compounds that merit further investigation.     

Cytogenetic biomonitoring of oral mucosa cells of crack cocaine users

The aim of the present study was to comparatively evaluate genomic damage (micronucleus) and cellular death (pyknosis, karyolysis, and karyorrhexis) in exfoliated oral mucosa cells from crack cocaine users by micronucleus test. A total of 30 crack cocaine users and 30 health controls (non-exposed individuals) were included in this setting. Individuals had epithelial cells from cheek mechanically exfoliated, placed in fixative, and dropped in clean slides, which were checked for the above nuclear phenotypes. The results pointed out significant statistical differences (p?<?0.05) of micronucleated oral mucosa cells from crack cocaine users. Exposure to crack cocaine caused an increase of other nuclear alterations closely related to cytotoxicity such as karyolysis in oral cells as well. In summary, these data indicate that crack cocaine is able to induce chromosomal breakage and cellular death in oral mucosa cells of users.     

Biological nitrogen and carbon removal in a gravity flow biomass concentrator reactor for municipal sewage treatment

A novel membrane system, the Biomass Concentrator Reactor (BCR), was evaluated as an alternative technology for the treatment of municipal wastewater. Because the BCR is equipped with a membrane whose average poresize is 20 μm (18–28 μm), the reactor requires low-pressure differential to operate (gravity). The effectiveness of this system was evaluated for the removal of carbon and nitrogen using two identical BCRs, identified as conventional and hybrid, that were operated in parallel. The conventional reactor was operated under full aerobic conditions (i.e., organic carbon and ammonia oxidation), while the hybrid reactor incorporated an anoxic zone for nitrate reduction as well as an aerobic zone for organic carbon and ammonia oxidation. Both reactors were fed synthetic wastewater at a flow rate of 71 L d^?1, which resulted in a hydraulic retention time of 9 h. In the case of the hybrid reactor, the recycle flow from the aerobic zone to the anoxic zone was twice the feed flow rate. Reactor performance was evaluated under two solids retention times (6 and 15 d). Under these conditions, the BCRs achieved nearly 100% mixed liquor solids separation with a hydraulic head differential of less than 2.5 cm. The COD removal efficiency was over 90%. Essentially complete nitrification was achieved in both systems, and nitrogen removal in the hybrid reactor was close to the expected value (67%).