Process hazards review applied to the use of anhydrous ammonia in agriculture: an example of chemical process safety for small business

Process hazards review (PHR) techniques have generally been applied by large, sophisticated companies in the nuclear, aerospace, and chemical process industries. There remains, however, a large population of smaller distributors and consumers of hazardous materials which could benefit equally from the application of PHR. These consumers unfortunately are generally less sophisticated and individually lack the necessary resources required to apply such state-of-the-art safety techniques.

Where common processes can be identified, it is possible to conduct a more generic PHR that will provide a sound technical basis for recognizing and preventing the development of hazards wherever these processes are used. Some facility-specific issues will always need to be considered, but the existence of the generic PHR should make the conduct of a PHR by each facility considerably easier and less costly.

Researchers from the National Institute for Occupational Safety and Health (NIOSH) contracted with DNV Technica Inc. to lead a hazard and operability study (HAZOP) of agricultural handling of anhydrous ammonia, from the receipt of ammonia at the retail distribution centre to the application of the ammonia by farmers to the fields. The multidisciplinary HAZOP team consisted of representatives from NIOSH, an agricultural chemical trade association, an ammonia producer, state ammonia facility inspectors, a retail distributor, and an equipment manufacturer. Several participants were part-time farmers with ammonia application experience.

Some specific aspects of applying the HAZOP technique in the context of this study, the findings obtained, and the plans to disseminate the important safety information developed during the course of the PHR are discussed. Finally, it is suggested that this approach could prove to be a useful addition to the product stewardship activities of chemical producers.     

Rejection of emerging organic micropollutants in nanofiltration-reverse osmosis membrane applications.

The rejection of emerging trace organics by a variety of commercial reverse osmosis (RO), nanofiltration (NF), and ultra-low-pressure RO (ULPRO) membranes was investigated using TFC-HR, NF-90, NF-200, TFC-SR2, and XLE spiral membrane elements (Koch Membrane Systems, Wilmington, Massachusetts) to simulate operational conditions for drinking-water treatment and wastewater reclamation. In general, the presence of effluent organic matter (EfOM) improved the rejection of ionic organics by tight NF and RO membranes, as compared to a type-II water matrix (adjusted by ionic strength and hardness), likely as a result of a decreased negatively charged membrane surface. Rejection of ionic pharmaceutical residues and pesticides exceeded 95% by NF-90, XLE, and TFC-HR membranes and was above 89% for the NF-200 membrane. Hydrophobic nonionic compounds, such as bromoform and chloroform, exhibited a high initial rejection, as a result of both hydrophobic-hydrophobic solute-membrane interactions and steric exclusion, but rejection decreased significantly after 10 hours of operation because of partitioning of solutes through the membranes. This resulted in a partial removal of disinfection byproducts by the RO membrane TFC-HR. In a type-II water matrix, the effect of increasing feed water recoveries on rejection of hydrophilic ionic and nonionic compounds was compound-dependent and not consistent for different membranes. The presence of EfOM, however, could neutralize the effect of hydrodynamic operating condition on rejection performance. The ULPRO and tight NF membranes were operated at lower feed pressure, as compared to the TFC-HR, and provided a product water quality similar to a conventional RO membrane, regarding trace organics of interest.     

Modelling of silica diffusion experiments with Si in Boom Clay

A mathematical model describing the dissolution of nuclear glass directly disposed in clay combines a first-order dissolution rate law with the diffusion of dissolved silica in clay. According to this model, the main parameters describing the long-term dissolution of the glass are ηR, the product of the diffusion accessible porosity η and the retardation factor R, and the apparent diffusion coefficient D_app of dissolved silica in clay.For determining the migration parameters needed for long-term predictions, four Through-Diffusion (T-D) experiments and one percolation test have been performed on undisturbed clay cores. In the Through-Diffusion experiments, the concentration decrease after injection of ³²Si (radioactive labelled silica) was measured in the inlet compartment. At the end of the T-D experiments, the clay cores were cut in thin slices and the activity of labelled silica in each slice was determined. The measured activity profiles for these four clay cores are well reproducible.Since no labelled silica could be detected in the outlet compartments, the Through-Diffusion experiments are fitted by two In-Diffusion models: one model assuming linear and reversible sorption equilibrium and a second model taking into account sorption kinetics. Although the kinetic model provides better fits, due to the sufficiently long duration of the experiments, both models give approximately similar values for the fit parameters. The single percolation test leads to an apparent diffusion coefficient value about two to three times lower than those of the Through-Diffusion tests.Therefore, dissolved silica appears to be strongly retarded in Boom Clay. A retardation factor R between 100 and 300 was determined. The corresponding in situ distribution coefficient K_d is in the range 25–75 cm³ g⁻¹. The apparent diffusion coefficient of dissolved silica in Boom Clay is estimated between 2×10⁻¹³ and 7×10⁻¹³ m² s⁻¹. The pore diffusion coefficient is in the range from 6×10⁻¹¹ to 1×10⁻¹⁰ m² s⁻¹.     

The importance of biological factors affecting trace metal concentration as revealed from accumulation patterns in co-occurring terrestrial invertebrates

As physicochemical properties of the soil highly influence the bioavailable fraction of a particular trace metal, measured metal body burdens in a particular species are often assumed to be more reliable estimators of the contamination of the biota. To test this we compared the Cd, Cu and Zn content of three spiders (generalist predators) and two amphipods (detritivores), co-occurring in seven tidal marshes along the river Schelde, between each other and with the total metal concentrations and the concentrations of four sequential extractions of the soils. Correlations were significant in only one case and significant site x species interactions for all metals demonstrate that factors affecting metal concentration were species and site specific and not solely determined by site specific characteristics. These results emphasize that site and species specific biological factors might be of the utmost importance in determining the contamination of the biota, at least for higher trophic levels. A hypothetical example clarifies these findings.     

Relating cadmium concentrations in three macrophyte-associated freshwater invertebrates to those in macrophytes,water and sediments

We found that Cd concentrations in three species of macrophyte-associated invertebrates (the gastropods Bithynia tentaculata and Physa gyrina, and the amphipod Gammarus fasciatus) collected at twenty sites along the St. Lawrence River were correlated with Cd concentrations in their main food source, i.e. macrophytes and associated periphyton. Cd in these invertebrates was not significantly correlated with Cd concentrations in the sediments (even when corrections for iron oxide or organic carbon content were applied) or to calculated free-cadmium concentrations in the water. Cd levels in juveniles of B. tentaculata were very tightly linked to Cd concentrations in macrophytes, which is consistent with the close relationship that these organisms have developed with macrophytes. Linear models predicting Cd levels in juveniles of B. tentaculata from Cd levels in different macrophyte species were strong (R2 = 0.69-0.90). Analysis of covariance on these models showed no statistical difference of slope or intercept for any of the macrophyte species, except Vallisneria americana. We suggest that the macrophyte-periphyton complex is a key link in the transfer of cadmium to some aquatic invertebrates in the littoral zone of the St. Lawrence River and that macrophytes and their associated epiphytes should also be used as biomonitors.     

Photolytic degradation of fluoroquinolone carboxylic acids in aqueous solution

Subsequent to irradiation with a xenon lamp simulating sunlight, fluoroquinolone carboxylic acids in aqueous solution form polar pyridone dicarboxylic and tricarboxylic acids. After liquid/liquid partition with chloroform/water these substances can be isolated by ion exchange chromatography of the aqueous phase. They can be regarded as intermediate compounds on the route to a complete photomineralization. The structural elucidation is performed by such mass spectroscopic methods as MS, GC/MS and HPLC/MS, whereby HPLC/MS shows the highest reliability. Additionally¹H- and¹³C-NMR measurements confirm the structure of the main polar degradation product.     

Crinoid phylogeny: a preliminary analysis (Echinodermata: Crinoidea)

We describe the first molecular and morphological analysis of extant crinoid high-level inter-relationships. Nuclear and mitochondrial gene sequences and a cladistically coded matrix of 30 morphological characters are presented, and analysed by phylogenetic methods. The molecular data were compiled from concatenated nuclear-encoded 18S rDNA, internal transcribed spacer 1, 5.8S rDNA, and internal transcribed spacer 2, together with part of mitochondrial 16S rDNA, and comprised 3,593 sites, of which 313 were parsimony-informative. The molecular and morphological analyses include data from the bourgueticrinid Bathycrinus; the antedonid comatulids Dorometra and Florometra; the cyrtocrinids Cyathidium, Gymnocrinus, and Holopus; the isocrinids Endoxocrinus, and two species of Metacrinus; as well as from Guillecrinus and Caledonicrinus, whose ordinal relationships are uncertain, together with morphological data from Proisocrinus. Because the molecular data include indel-rich regions, special attention was given to alignment procedure, and it was found that relatively low, gene-specific, gap penalties gave alignments from which congruent phylogenetic information was obtained from both well-aligned, indel-poor and potentially misaligned, indel-rich regions. The different sequence data partitions also gave essentially congruent results. The overall direction of evolution in the gene trees remains uncertain: an asteroid outgroup places the root on the branch adjacent to the slowly evolving isocrinids (consistent with palaeontological order of first appearances), but maximum likelihood analysis with a molecular clock places it elsewhere. Despite lineage-specific rate differences, the clock model was not excluded by a likelihood ratio test. Morphological analyses were unrooted. All analyses identified three clades, two of them generally well-supported. One well-supported clade (BCG) unites Bathycrinus and Guillecrinus with the representative (chimaeric) comatulid in a derived position, suggesting that comatulids originated from a sessile, stalked ancestor. In this connection it is noted that because the comatulid centrodorsal ossicle originates ontogenetically from the column, it is not strictly correct to describe comatulids as unstalked crinoids. A second, uniformly well-supported clade contains members of the Isocrinida, while the third clade contains Gymnocrinus, a well-established member of the Cyrtocrinida, together with the problematic taxon Caledonicrinus, currently classified as a bourgueticrinid. Another cyrtocrinid, Holopus, joins this clade with only weak molecular, but strong morphological support. In one morphological analysis Proisocrinus is weakly attached to the isocrinid clade. Only an unusual, divergent 18S rDNA sequence was obtained from the morphologically strange cyrtocrinid Cyathidium. Although not analysed in detail, features of this sequence suggested that it may be a PCR artefact, so that the apparently basal position of this taxon requires confirmation. If not an artefact, Cyathidium either diverged from the crinoid stem much earlier than has been recognised hitherto (i.e., it may be a Palaeozoic relic), or it has an atypically high rate of molecular evolution.Electronic Supplementary Material Supplementary material is available in the online version of this article at Communicated by J.P. Thorpe, Port Erin     

Male responsiveness to infant distress calls in free-ranging vervet monkeys

Summary Playback experiments were conducted of five groups of free-ranging vervet monkeys (Cercopithecus aethiops) to determine whether an adult male's responsiveness to infant distress calls was a function of (1) paternal certainty, (2) dominance rank, (3) predator presence, (4) number of males, (5) number of infants, (6) infant's mother's rank and/or (7) infant's age. Results from these experiments reveal that paternal certainty was the only factor that could directly explain the differences between males in the duration of response to distress calls.     

Cellular localisation of secondary metabolites isolated from the Caribbean sponge <Emphasis Type="Italic">Plakortis simplex</Emphasis>

The Caribbean sponge, Plakortis simplex, is known to contain a large array of secondary metabolites, including the antimalarial polyketide plakortin, several unusual glycolipids, and some hopanoids, which closely resemble typical bacterial metabolites. The hypothesis that they could be products of bacterial metabolism was tested by localizing specific metabolites in cells using physical separation of sponge cells, bacterial symbionts and supernatant by differential centrifugation. The obtained fractions were analysed separately for the typical P. simplex metabolites by NMR and mass spectrometry, and most of them were shown to be present in the bacterial cells but not in the sponge cells. In addition, PCR screening showed that the biosynthetic pathway for glycosphingolipids was present in the bacterial cells. Isolation of a Sphingomonas strain PS193 from P. simplex and subsequent glycosphingolipid analysis resulted in the detection of a known glycosphingolipid, GSL-1, that did, however, not match the glycosphingolipid profile of P. simplex. Therefore, it is unlikely that Sphingomonas strain PS193 is an abundant member of the microbial community associated with P. simplex. Other glycosphingolipid producing bacteria in P. simplex remain to be identified. In conclusion, this study provides experimental evidence that the glycolipids and hopanoids and possibly also the polyketide plakortin are produced by microbial symbionts rather than the sponge from which the metabolites were originally isolated.