Influence of competing inorganic cations on the ion exchange equilibrium of the monovalent organic cation metoprolol on natural sediment

The aim of this study was to systematically investigate the influence of the mono- and divalent inorganic ions Na⁺ and Ca²⁺ on the sorption behavior of the monovalent organic cation metoprolol on a natural sandy sediment at pH = 7. Isotherms for the beta-blocker metoprolol were obtained by sediment–water batch tests over a wide concentration range (1–100 000 μg L^?1). Concentrations of the competing inorganic ions were varied within freshwater relevant ranges. Data fitted well with the Freundlich sorption model and resulted in very similar Freundlich exponents (n = 0.9), indicating slightly non-linear behavior. Results show that the influence of Ca²⁺ compared to Na⁺ is more pronounced. A logarithmic correlation between the Freundlich coefficient K_Fr and the concentration or activity of the competing inorganic ions was found allowing the prediction of metoprolol sorption on the investigated sediment at different electrolyte concentrations. Additionally, the organic carbon of the sediment was completely removed for investigating the influence of organic matter on the sorption of metoprolol. The comparison between the experiments with and without organic carbon removal revealed no significant contribution of the organic carbon fraction (0.1%) to the sorption of metoprolol on the in this study investigated sediment. Results of this study will contribute to the development of predictive models for the transport of organic cations in the subsurface.     

Uptake and accumulation of naphthalene by the oyster Ostrea edulis,in a flow-through system

A flow-through system was used to follow naphthalene and naphthalene metabolite accumulation in the seawater and in the tissue of the oyster Ostrea edulis. After 72 h, 82.5% of the naphthalene carbon was recovered from the system. Glucose was added to seawater to stimulate the pathways of glucose metabolism in the oysters. Streptomycin (100 ppm) reduced microbial oxidation of naphthalene and glucose, and reduced bacterial growth. However, even in the presence of streptomycin, microbial oxidation of naphthalene was considerable. The main oxidation product recovered from seawater was ¹⁴CO₂. Radioactivity was also associated with compounds which separated by TLC with 2- and 1- naphthol. The pattern of naphthalene uptake and accumulation in oyster tissues was relatively constant after only a few hours of exposure to naphthalene. The potential of tissues to accumulate naphthalene was shown to be a function of multiple variables such as nutritional state, lipid concentration, length of exposure to naphthalene, and the external naphthalene concentration. Carbon-14-labeled metabolites derived from ¹⁴C-naphthalene were consistently recovered from digests of the oyster tissues. Non-CO₂ alkaline-soluble substances were the primary metabolites. Hexane-extractable substances, which separated by TLC with known standards of 2- and 1- naphthol, were consistently recovered from seawater and tissue digests. It was not possible to conclude that these metabolites were a result of naphthalene metabolism by oyster enzyme systems.     

Sorption influenced transport of ionizable pharmaceuticals onto a natural sandy aquifer sediment at different pH

The pH-dependent transport of eight selected ionizable pharmaceuticals was investigated by using saturated column experiments. Seventy-eight different breakthrough curves on a natural sandy aquifer material were produced and compared for three different pH levels at otherwise constant conditions. The experimentally obtained K_OC data were compared with calculated K_OC values derived from two different log K_OW-log K_OC correlation approaches. A significant pH-dependence on sorption was observed for all compounds with pK_a in the considered pH range. Strong retardation was measured for several compounds despite their hydrophilic character. Besides an overall underestimation of K_OC, the comparison between calculated and measured values only yields meaningful results for the acidic and neutral compounds. Basic compounds retarded much stronger than expected, particularly at low pH when their cationic species dominated. This is caused by additional ionic interactions, such as cation exchange processes, which are insufficiently considered in the applied K_OC correlations.     

Creating safer workplaces: assessing the determinants and role of safety climate

PROBLEM: Although there has been considerable interest in safety climate, relatively little attention has been given to the factors that determine safety climate or to testing the hypothesized mediating role of safety climate with respect to safety-related outcomes. METHOD: Questionnaire responses were obtained from 2,208 employees of a large national retail chain in 21 different locations. RESULTS: After controlling for demographic variables, three factors: environmental conditions, safety-related policies and programs, and general organizational climate, accounted for 55% of the variance in perceived safety climate. Interestingly, organizational climate made a significant contribution to safety climate, even after controlling for the other more safety-relevant variables. Partial correlations showed that safety policies and programs had the largest observed correlation with safety climate, followed by two of the dimensions of organizational climate (communication and organizational support). Using Baron and Kenny's (J. Pers. Soc. Psychol. 51 (1986) 1173) procedures, the principal effects of the various work situation factors on perceived safety at work were found to be direct rather than mediated by safety climate. Safety climate influenced perceived safety at work, but its role as a mediator was limited. IMPACT ON INDUSTRY: These results are discussed in terms of other recent findings on safety climate and the growing interest in understanding management and organizational factors in the context of workplace safety.     

Combining target analysis with sum parameters—a comprehensive approach to determine sediment contamination with PFAS and further fluorinated substances

Recent studies aiming at a fluorine mass balance analysis in sediments combined the determination of extractable organic fluorine (EOF) with target analysis. They reported high fractions of unidentified organic fluorine (UOF) compounds, as the target analysis covers only a limited number of per- and polyfluoroalkyl substances (PFAS). For this reason, in this study, a comprehensive approach was used combining target analysis with an extended PFAS spectrum, the EOF and a modified total oxidisable precursor (TOP) assay, which includes trifluoroacetic acid, to determine the PFAS contamination in sediments (n=41) and suspended solids (n=1) from water bodies in Northern Germany (Lower Saxony). PFAS are ubiquitous in the sediments (detected in 83% of the samples). Perfluorinated carboxylic acids (PFCAs) were found in 64% of the samples; perfluorinated sulfonic acids (PFSAs) were detected less frequently (21%), with the highest concentration observed for perfluorooctanesulfonic acid (PFOS). Levels of precursors and substitutes were lower. Applying the TOP assay resulted in an increase in PFCAs in 43% of the samples analysed. In most cases, target analysis and the TOP assay could not account for the EOF concentrations measured. However, as the fraction of UOF decreased significantly, the application of the TOP assay in fluorine mass balance analysis proved to be an important tool in characterising the PFAS contamination of riverine sediments.

     

Summer cover crops reduce atrazine leaching to shallow groundwater in southern Florida

At Florida's southeastern tip, sweet corn (Zea Mays) is grown commercially during winter months. Most fields are treated with atrazine (6-chloro-N-ethyl-N'-[1-methylethyl]-1,3,5-triazine-2,4-diamine). Hydrogeologic conditions indicate a potential for shallow groundwater contamination. This was investigated by measuring the parent compound and three degradates--DEA (6-chloro-N-[1-methylethyl]-1,3,5-triazine-2,4-diamine), DIA (6-chloro-N-ethyl)-1,3,5-triazine-2,4-diamine, and HA (6-hydroxy-N-[1-methylethyl]-1,3,5-triazine-2,4-diamine)--in water samples collected beneath sweet corn plots treated annually with the herbicide. During the study, a potential mitigation measure (i.e., the use of a cover crop, Sunn Hemp [Crotalaria juncea L.], during summer fallow periods followed by chopping and turning the crop into soil before planting the next crop) was evaluated. Over 3.5 yr and production of four corn crops, groundwater monitoring indicated leaching of atrazine, DIA, and DEA, with DEA accounting for more than half of all residues in most samples. Predominance of DEA, which increased after the second atrazine application, was interpreted as an indication of rapid and extensive atrazine degradation in soil and indicated that an adapted community of atrazine degrading organisms had developed. A companion laboratory study found a sixfold increase in atrazine degradation rate in soil after three applications. Groundwater data also revealed that atrazine and degradates concentrations were significantly lower in samples collected beneath cover crop plots when compared with concentrations below fallow plots. Together, these findings demonstrated a relatively small although potentially significant risk for leaching of atrazine and its dealkylated degradates to groundwater and that the use of a cover crop like Sunn Hemp during summer months may be an effective mitigation measure.     

Characterization of non-extractable ¹⁴C- and ¹³C-sulfadiazine residues in soil including simultaneous amendment of pig manure

Recently, we reported on soil fate of SDZ residues amended with pig manure treated with 1?C-labeled sulfadiazine 1?C-SDZ). The first objective of the present study was to determine whether this strategy can be substituted by application of 1?C-SDZ to soil. The second objective was to characterize non-extractable SDZ residues by fractionation, size exclusion chromatography (SEC) and solid state 13C-NMR. The fate of 1?C-SDZ was examined for 28 d, using two soils with and without amendment of pig manure. Mineralization of 1?C-SDZ was low; extractable residues decreased to 7-30%. Compared to the previous study, results were similar. 1?C-SDZ derived bound radioactivity was found in HCl-washings, fulvic, humic acids and humin. According to SEC, one bound 1?C portion (70%) co-eluted with fulvic acids (above 910 g mol?1); the other consisted of adsorbed/entrapped 1?C-SDZ. The 13C-SDZ study was performed for 30 d; humic acids were examined by 13C-NMR. A signal (100-150 ppm) was referred to 13C-SDZ. SEC and 13C-NMR demonstrated rapid integration of SDZ into humics.     

Influence of home characteristics on airborne and dustborne endotoxin and β-D-glucan

The aim of this study was to assess the associations between airborne and dustborne microbial contaminants (endotoxin and β-D-glucan) and estimate the effects of home characteristics on exposure levels of these microbial contaminants. Endotoxin and β-D-glucan concentrations in airborne inhalable particles, airborne PM1 (<1 μm) and vacuumed dust from 184 residential homes were determined using specific Limulus amebocyte assays. Home characteristics were recorded by visual inspection and questionnaires. Linear regression and correlation analyses were performed. Inhalable endotoxin correlated with dust endotoxin (r = 0.34, p < 0.001) and PM1 endotoxin (r = 0.33, p < 0.001). Inhalable β-D-glucan correlated with dust β-D-glucan (r = 0.18, p < 0.01), but not with PM1 β-D-glucan. Significant correlation was also found between PM1 and dust concentrations for endotoxin (r = 0.26, p < 0.001), but not for β-D-glucan. Multivariate regression analyses showed only one significant association between airborne contaminants and environmental characteristics: inhalable β-D-glucan was positively associated with relative humidity with an effect size (change in the dependent variable corresponding to a unit increase in the independent variable) of 2.32 and p < 0.05. In contrast, several associations were found between dust concentrations and environmental characteristics. Dust endotoxin was positively associated with temperature (2.87, p < 0.01) and number of inhabitants (2.76, p < 0.01), whereas dust β-D-glucan was inversely associated with the presence of dogs (-2.24, p < 0.05) and carpet (-3.05, p < 0.01) in the home. In conclusion, dustborne contaminants were more strongly affected by home characteristics than airborne contaminants. Furthermore, even though statistically significant, the correlations between airborne and dustborne contaminants were weak. This indicates that airborne concentrations cannot be reliably predicted based on dustborne concentrations.