Biological monitoring of occupational exposure to polycyclic aromatic hydrocarbons in prebake smelting

In 1984, the International Agency for Research on Cancer determined that working in the primary aluminium production process was associated with exposure to certain polycyclic aromatic hydrocarbons (PAHs) that are probably carcinogenic to humans. Key sources of PAH exposure within the occupational environment of a prebake aluminium smelter are processes associated with use of coal-tar pitch. Despite the potential for exposure via inhalation, ingestion and dermal adsorption, to date occupational exposure limits exist only for airborne contaminants. This study, based at a prebake aluminium smelter in Queensland, Australia, compares exposures of workers who came in contact with PAHs from coal-tar pitch in the smelter’s anode plant (n = 69) and cell-reconstruction area (n = 28), and a non-production control group (n = 17). Literature relevant to PAH exposures in industry and methods of monitoring and assessing occupational hazards associated with these compounds are reviewed, and methods relevant to PAH exposure are discussed in the context of the study site. The study utilises air monitoring of PAHs to quantify exposure via the inhalation route and biological monitoring of 1-hydroxypyrene (1-OHP) in urine of workers to assess total body burden from all routes of entry. Exposures determined for similar exposure groups, sampled over three years, are compared with published occupational PAH exposure limits and/or guidelines. Results of paired personal air monitoring samples and samples collected for 1-OHP in urine monitoring do not correlate. Predictive ability of the benzene-soluble fraction (BSF) in personal air monitoring in relation to the 1-OHP levels in urine is poor (adjusted R2 < 1%) even after adjustment for potential confounders of smoking status and use of personal protective equipment. For static air BSF levels in the anode plant, the median was 0.023 mg/m3 (range 0.002–0.250), almost twice as high as in the cell-reconstruction area (median = 0.013 mg/m3, range 0.003–0.154). In contrast, median BSF personal exposure in the anode plant was 0.036 mg/m3 (range 0.003–0.563), significantly lower than the median measured in the reconstruction area (0.054 mg/m3, range 0.003–0.371) (p = 0.041). The observation that median 1-OHP levels in urine were significantly higher in the anode plant than in the reconstruction area (6.62 µmol/mol creatinine, range 0.09–33.44 and 0.17 µmol/mol creatinine, range 0.001–2.47, respectively) parallels the static air measurements of BSF rather than the personal air monitoring results (p < 0.001). Results of air measurements and biological monitoring show that tasks associated with paste mixing and anode forming in the forming area of the anode plant resulted in higher PAH exposure than tasks in the non-forming areas; median 1-OHP levels in urine from workers in the forming area (14.20 µmol/mol creatinine, range 2.02–33.44) were almost four times higher than those obtained from workers in the non-forming area (4.11 µmol/mol creatinine, range 0.09–26.99; p < 0.001). Results justify use of biological monitoring as an important adjunct to existing measures of PAH exposure in the aluminium industry. Although monitoring of 1-OHP in urine may not be an accurate measure of biological effect on an individual, it is a better indicator of total PAH exposure than BSF in air. In January 2005, interim study results prompted a plant management decision to modify control measures to reduce skin exposure. Comparison of 1-OHP in urine from workers pre- and post-modifications showed substantial downward trends. Exposure via the dermal route was identified as a contributor to overall dose. Reduction in 1-OHP urine concentrations achieved by reducing skin exposure demonstrate the importance of exposure via this alternative pathway. Finally, control measures are recommended to ameliorate risk associated with PAH exposure in the primary aluminium production process, and suggestions for future research include development of methods capable of more specifically monitoring carcinogenic constituents of PAH mixtures, such as benzo[a]pyrene.

Testing for the non-separability of bi-ambiguous compounds

Separability is a concept that is very difficult to define, and yet much of our scientific method is implicitly based upon the assumption that systems can sensibly be reduced to a set of interacting components. This paper examines the notion of separability in the creation of bi-ambiguous compounds that is based upon the CHSH and CH inequalities. It reports results of an experiment showing that violations of the CHSH and CH inequality can occur in human conceptual combination.

Metal Contaminants in Leachate from Sanitary Landfills

The uncontrolled disposal of solid wastes poses an immediate threat to public health and a long term threat to the environmental well being of future generations. Solid waste is waste resulting from human activities that is solid and unwanted (Peavy et al., 1985). If unmanaged, dumped solid wastes generate liquid and gaseous emissions that are detrimental to the environment. This can lead to a serious form of contamination known as metal contamination, which poses a risk to human health and ecosystems. For example, some heavy metals (cadmium, chromium compounds, and nickel tetracarbonyl) are known to be highly toxic, and are aggressive at elevated concentrations. Iron, copper, and manganese can cause staining, and aluminium causes depositions and discolorations. In addition, calcium and magnesium cause hardness in water causing scale deposition and scum formation. Though not a metal but a metalloid, arsenic is poisonous at relatively high concentrations and when diluted at low concentrations causes skin cancer. Normally, metal contaminants are found in a dissolved form in the liquid percolating through landfills. Because average metal concentrations from full-scale landfills, test cells, and laboratory studies have tended to be generally low, metal contamination originating from landfills is not generally considered a major concern (Kjeldsen et al., 2002; Christensen et al., 1999). However, a number of factors make it necessary to take a closer look at metal contaminants from landfills. One of these factors relates to variability. Landfill leachate can have different qualities depending on the weather and operating conditions. Therefore, at one moment in time, metal contaminant concentrations may be quite low, but at a later time these concentrations could be quite high. Also, these conditions relate to the amount of leachate that is being generated. Another factor is biodiversity. It cannot be assumed that a particular metal contaminant is harmless to flora and fauna (including micro organisms) just because it is harmless to human health. This has significant implications for ecosystems and the environment. Finally, there is the moral factor. Because uncertainty surrounds the potential effects of metal contamination, it is appropriate to take precautions to prevent it from taking place. Consequently, it is necessary to have good scientific knowledge (empirically supported) to adequately understand the extent of the problem and improve the way waste is being disposed of

Anhydrous 1:1 proton-transfer compounds of isonipecotamide with picric acid and 3,5-dinitrosalicylic acid: 4-carbamoylpiperidinium 2,4,6-trinitrophenolate and two polymorphs of 4-carbamoylpiperidinium 2-carboxy-4,6-dinitrophenolate

The structures of the anhydrous 1:1 proton-transfer compounds of isonipecotamide (4-carbamoylpiperidine) with picric acid and 3,5-dinitrosalicylic acid, namely 4-carbamoylpiperidinium 2,4,6-trinitrophenolate, C6H13N2O8+ C6H2N3O7- (I) and 4-carbamoylpiperidinium 2-carboxy-4,6-dinitrophenolate, C6H13N2O8+ C7H3N2O7-: two forms, the monoclinic alpha-polymorph (II) and the triclinic beta-polymorph (III) have been determined at 200 K. All compounds form hydrogen-bonded structures, one-dimensional in (II), two-dimensional in (I) and three-dimensional in (III). In (I), the cations form centrosymmetric cyclic head-to-tail hydrogen-bonded homodimers [graph set R2/2(14)] through lateral duplex piperidinium N---H...O(amide) interactions. These dimers are extended into a two-dimensional network structure through further interactions with anion phenolate-O and nitro-O acceptors, including a direct symmetric piperidinium N-H...O(phenol),O(nitro) cation--anion association [graph set R2/1(6)]. The monoclinic polymorph (II) has a similar R2/1(6) cation-anion hydrogen-bonding interaction to (I) but with an additional conjoint symmetrical R1/2(4) interaction as well as head-to-tail piperidinium N-H...O(amide) O hydrogen bonds and amide N-H...O(carboxyl) hydrogen bonds, give a network structure which include large R3/4(20) rings. The hydrogen bonding in the triclinic polymorph (III) is markedly different from that of monoclinic (II). The asymmetric unit contains two independent cation-anion pairs which associate through cyclic piperidinium N-H...O,O'(carboxyl) interactions [graph set R2/1(4)]. The cations also show the zig-zag head-to-tail piperidinium N-H...O(amide) hydrogen-bonded chain substructures found in (II) but in addition feature amide N-H...O(nitro) and O(phenolate) and amide N-H...O(nitro) associations. As well there is a centrosymmetric double-amide N-H...O(carboxyl) bridged bis(cation-anion) ring system [graph set R2/4(8)] in the three-dimensional framework. The structures reported here demonstrate the utility of the isonipecotamide cation as a synthon with previously unrecognized potential for structure assembly applications. Furthermore, the structures of the two polymorphic 3,5-dinitrosalicylic acid salts show an unusual dissimilarity in hydrogen-bonding characteristics, considering that both were obtained from identical solvent systems.

Hydrogen bonding in the anhydrous 1:1 proton-transfer compounds of isonipecotamide with nitro-substituted benzoic acids: the salts of the three isomeric mononitrobenzoic acids and of 3,5-dinitrobenzoic acid

The structures of the anhydrous 1:1 proton-transfer compounds of isonipecotamide (piperidine-4-carboxamide) with the three isomeric mononitro-substituted benzoic acids and 3,5-dinitrobenzoic acid, namely 4-carbamoylpiperidinium 2-nitrobenzoate (I), 4-carbamoylpiperidinium 3-nitrobenzoate (II), 4-carbamoylpiperidinium 4-nitrobenzoate (III), (C6H13N2O+ C7H4NO4-) and 4-carbamoylpiperidinium 3,5-dinitrobenzoate (IV) (C6H13N2O+ C7H5N2O6-)respectively, have been determined at 200 K. All salts form hydrogen-bonded structures: three-dimensional in (I), two-dimensional in (II) and (III) and one-dimensional in (IV). Featured in the hydrogen bonding of three of these [(I), (II) and (IV)] is the cyclic head-to-head amide--amide homodimer motif [graph set R2/2~(8)] through a duplex N---H...O association, the dimer then giving structure extension via either piperidinium or amide H-donors and carboxylate-O and in some examples [(II) and (IV)], nitro-O atom acceptors. In (I), the centrosymmetric amide-amide homodimers are expanded laterally through N-H...O hydrogen bonds via cyclic R2/4(8) interactions forming ribbons which extend along the c cell direction. These ribbons incorporate the 2-nitrobenzoate cations through centrosymmetric cyclic piperidine N-H...O(carboxyl) associations [graph set R4/4(12)], giving inter-connected sheets in the three-dimensional structure. In (II) in which no amide-amide homodimer is present, duplex piperidinium N-H...O(amide) hydrogen-bonding homomolecular associations [graph set R2/2(14)] give centrosymmetric head-to-tail dimers. Structure extension occurs through hydrogen-bonding associations between both the amide H-donors and carboxyl and nitro O-acceptors as well as a three-centre piperidinium N-H...O,O'(carboxyl) cyclic R2/1(4) association giving the two-dimensional network structure. In (III), the centrosymmetric amide-amide dimers are linked through the two carboxyl O-atom acceptors of the anions via bridging piperidinium and amide N-H...O,O'...H-N(amide) hydrogen bonds giving the two-dimensional sheet structure which features centrosymmetric cyclic R4/4(12) associations. In (IV), the amide-amide dimer is also centrosymmetric with the dimers linked to the anions through amide N-H...O(nitro) interactions. The piperidinium groups extend the structure into one-dimensional ribbons via N-H...O(carboxyl) hydrogen bonds. The structures reported here further demonstrate the utility of the isonipecotamide cation in molecular assembly and highlight the efficacy of the cyclic R2/2(8) amide-amide hydrogen-bonding homodimer motif in this process and provide an additional homodimer motif type in the head-to-tail R2/2(14) association.

Hydrogen bonding in proton-transfer compounds of 5-sulfosalicylic acid with a series of aliphatic nitrogen Lewis bases

The crystal structures of the proton-transfer compounds of 5-sulfosalicylic acid (3-carboxy-4-hydroxybenzenesulfonic acid) with the aliphatic nitrogen Lewis bases, hydroxylamine, triethylamine, pyrrolidine, morpholine, N-methylmorpholine and piperazine, viz. hydroxyammonium 3-carboxy-4-hydroxybenzenesulfonate (1), triethylaminium 3-carboxy-4-hydroxybenzenesulfonate (2), pyrrolidinium 3-carboxy-4-hydroxybenzenesulfonate monohydrate (3), morpholinium 3-carboxy-4-hydroxybenzenesulfonate monohydrate (4), N-methylmorpholinium 3-carboxy-4-hydroxybenzenesulfonate monohydrate (5) and piperazine-1,4-diium bis(3-carboxy-4-hydroxybenzenesulfonate) hexahydrate (6) have been determined and their comparative structural features and hydrogen-bonding patterns described. Crystals of 4 are triclinic, space group P-1 while the remainder are monoclinic with space group either P21/c (1 - 3) or P21/n (5, 6). Unit cell dimensions and contents are: for 1, a = 5.0156(3), b = 10.5738(6), c = 18.4785(9) Å, β = 96.412(5)o, Z = 4; for 2, a = 8.4998(4), b = 12.3832(6), c = 15.4875(9) Å, β = 102.411(5)o, Z = 4; for 3, a = 6.8755(2), b = 15.5217(4), c = 12.8335(3) Å, β = 92.074(2)o, Z = 4; for 4, a = 6.8397(2), b = 12.9756(5), c = 15.8216(6) Å, α = 90.833(3), β = 95.949(3), γ = 92.505(3)o, Z = 4; for 5, a = 7.0529(3), b = 13.8487(7), c = 15.6448(6) Å, β = 90.190(6)o, Z = 4; for 6, a = 7.0561(2), b = 15.9311(4), c = 12.2102(3) Å, β = 100.858(3)o, Z = 2. The hydrogen bonding generates structures which are either two-dimensional (2 and 5) or three-dimensional (1, 3, 4 and 6). Compound 6 represents the third reported structure of a salt of 5-sulfosalicylic acid having a dicationic piperazine species.

Raman spectroscopy of hydrogene-arsenate group (AsO3OH) in solid-state compounds: cobalt mineral phase burgessite Co2(H2O)4[AsO3OH]2•H2O

Raman spectrum of burgessite, Co2(H2O)4[AsO3OH]2.H2O was studied, interpreted and compared with its infrared spectrum. The stretching and bending vibrations of (AsO3) and As-OH units together with the stretching, bending and libration modes of water molecules and hydroxyl ions were assigned. The range of O-H...O hydrogen bond lengths was inferred from the Raman and infrared spectra of burgessite. The presence of (AsO3OH)2- units in the crystal structure of burgessite was proved in agreement with its recently solved crystal structure. Raman and infrared spectra of erythrite inferred from the RRUFF database are used for comparison.

Apoptosis is induced in Chlamydia trachomatis infected HEp-2 cells by the addition of a combination innate immune activation compounds and the inhibitor wedelolactone

Problem: Innate immune activation of human cells, for some intracellular pathogens, is advantageous for vacuole morphology and pathogenic viability. It is unknown whether innate immune activation is advantageous to Chlamydia trachomatis viability. ----- ----- Method of study: Innate immune activation of HEp-2 cells during Chlamydia infection was conducted using lipopolysaccharide (LPS), polyI:C, and wedelolactone (innate immune inhibitor) to investigate the impact of these conditions on viability of Chlamydia. ----- ----- Results: The addition of LPS and polyI:C to stimulate activation of the two distinct innate immune pathways (nuclear factor kappa beta and interferon regulatory factor) had no impact on the viability of Chlamydia. However, when compounds targeting either pathway were added in combination with the specific innate immune inhibitor (wedelolactone) a major impact on Chlamydia viability was observed. This impact was found to be due to the induction of apoptosis of the HEp-2 cells under these conditions. ----- ----- Conclusion: This is the first time that induction of apoptosis has been reported in C. trachomatis-infected cells when treated with a combination of innate immune activators and wedelolactone.

Reduction of nitroaromatic compounds on supported gold nanoparticles by visible and ultraviolet light

Shedding light: Nitroaromatic compounds on gold nanoparticles (3 wt %) supported on ZrO2 can be reduced directly to the corresponding azo compounds when illuminated with visible light or ultraviolet light at 40 °C (see picture). The process occurs with high selectivity and at ambient temperature and pressure, and enables the selection of intermediates that are unstable in thermal reactions.

Raman spectroscopy of hydrogen arsenate group (AsO3OH)2− in solid-state compounds: cobalt-containing zinc arsenate mineral, koritnigite (Zn,Co)(AsO3OH)·H2O

Raman spectra of two well-defined types of koritnigite crystals from the Jáchymov ore district, Czech Republic, were recorded and interpreted. No substantial differences were observed between both crystal types. Observed Raman bands were attributed to the (AsO3OH)2- stretching and bending vibrations, stretching and bending vibrations of water molecules and hydroxyl ions. Non-interpreted Raman spectra of koritnigite from the RRUFF database, and published infrared spectra of cobaltkoritnigite were used for comparison. The O-H...O hydrogen bond lengths in the crystal structure of koritnigite were inferred from the Raman spectra and compared with those derived from the X-ray single crystal refinement. The presence of (AsO3OH)2- units in the crystal structure of koritnigite was proved from the Raman spectra which supports the conclusions of the X-ray structure analysis.

Analysis of the build-up of semi and non volatile organic compounds on urban roads

Vehicular traffic in urban areas may adversely affect urban water quality through the build-up of traffic generated semi and non volatile organic compounds (SVOCs and NVOCs) on road surfaces. The characterisation of the build-up processes is the key to developing mitigation measures for the removal of such pollutants from urban stormwater. An in-depth analysis of the build-up of SVOCs and NVOCs was undertaken in the Gold Coast region in Australia. Principal Component Analysis (PCA) and Multicriteria Decision tools such as PROMETHEE and GAIA were employed to understand the SVOC and NVOC build-up under combined traffic scenarios of low, moderate, and high traffic in different land uses. It was found that congestion in the commercial areas and use of lubricants and motor oils in the industrial areas were the main sources of SVOCs and NVOCs on urban roads, respectively. The contribution from residential areas to the build-up of such pollutants was hardly noticeable. It was also revealed through this investigation that the target SVOCs and NVOCs were mainly attached to particulate fractions of 75 to 300 µm whilst the redistribution of coarse fractions due to vehicle activity mainly occurred in the >300 µm size range. Lastly, under combined traffic scenario, moderate traffic with average daily traffic ranging from 2300 to 5900 and average congestion of 0.47 was found to dominate SVOC and NVOC build-up on roads.

Prediction model of the buildup of volatile organic compounds on urban roads

A model to predict the buildup of mainly traffic-generated volatile organic compounds or VOCs (toluene, ethylbenzene, ortho-xylene, meta-xylene, and para-xylene) on urban road surfaces is presented. The model required three traffic parameters, namely average daily traffic (ADT), volume to capacity ratio (V/C), and surface texture depth (STD), and two chemical parameters, namely total suspended solid (TSS) and total organic carbon (TOC), as predictor variables. Principal component analysis and two phase factor analysis were performed to characterize the model calibration parameters. Traffic congestion was found to be the underlying cause of traffic-related VOC buildup on urban roads. The model calibration was optimized using orthogonal experimental design. Partial least squares regression was used for model prediction. It was found that a better optimized orthogonal design could be achieved by including the latent factors of the data matrix into the design. The model performed fairly accurately for three different land uses as well as five different particle size fractions. The relative prediction errors were 10–40% for the different size fractions and 28–40% for the different land uses while the coefficients of variation of the predicted intersite VOC concentrations were in the range of 25–45% for the different size fractions. Considering the sizes of the data matrices, these coefficients of variation were within the acceptable interlaboratory range for analytes at ppb concentration levels.