The influence of diesel—truck exhaust particles on the kinetics of the atmospheric oxidation of dissolved sulfur dioxide by oxygen

The automobile exhausts are one of the major sources of particulate matter in urban areas and these particles are known to influence the atmospheric chemistry in a variety of ways. Because of this, the oxidation of dissolved sulfur dioxide by oxygen was studied in aqueous suspensions of particulates, obtained by scraping the particles deposited inside a diesel truck exhaust pipe (DEP). A variation in pH showed the rate to increase with increase in pH from 5.22 to about ～6.3 and to decrease thereafter becoming very slow at pH?=?8.2. In acetate-buffered medium, the reaction rate was higher than the rate in unbuffered medium at the same pH. Further, the rate was found to be higher in suspension than in the leachate under otherwise identical conditions. And, the reaction rate in the blank reaction was the slowest. This appears to be due to catalysis by leached metal ions in leachate and due to catalysis by leached metal ions and particulate surface both in suspensions. The kinetics of dissolved SO₂ oxidation in acetate-buffered medium as well as in unbuffered medium at pH?=?5.22 were defined by rate law: k _obs ?=?k ₀?+?k _cat [DEP], where k _obs and k ₀ are observed rate constants in the presence and the absence of DEP and k _cat is the rate constant for DEP-catalyzed pathway. At pH?=?8.2, the reaction rate was strongly inhibited by DEP in buffered and unbuffered media. Results suggest that the DEP would have an inhibiting effect in those areas where rainwater pH is 7 or more. These results at high pH are of particular significance to the Indian subcontinent, because of high rainwater pH. Conversely, it indicates the DEP to retard the oxidation of dissolved SO₂ and control rainwater acidification.

     

Effects of soil moisture depletion on vegetable crop uptake of pharmaceuticals and personal care products (PPCPs)

Agricultural crops have a long history of being irrigated with recycled wastewater (RW). However, its use on vegetable crops has been of concern due to the potential prevalence of microcontaminants, such as pharmaceuticals and personal care products (PPCPs) in the latter, which represents a possible health hazard to consumers. We investigated the uptake of three PPCPs (atenolol, diclofenac, and ofloxacin), at three different concentrations in irrigation water (0.5, 5, and 25 μg L^?1) in relation to three varying volumetric soil moisture depletion levels of 14 % (?4.26 kPa), 10 % (?8.66 kPa), and 7 % (?18.37 kPa) by various vegetable crop species. Experiments were conducted in a split-split block completely randomized design. PPCPs were extracted using a developed method of accelerated solvent extraction and solid phase extraction and analyzed via liquid chromatography mass spectrometry (LCMS). Results indicate that all treated crops were capable of PPCP uptake at nanogram per gram concentrations independent of the applied soil moisture depletion levels and PPCP concentrations. Ofloxacin was the chemical with the highest uptake amounts, followed by atenolol and then diclofenac. Although the results were not statistically significant, higher concentrations of PPCPs were detected in plants maintained under higher soil moisture levels of 14 % (?4.26 kPa).     

Identification of a novel hydroxylated metabolite of 2,2′,3,5′,6-pentachlorobiphenyl formed in whole poplar plants

Polychlorinated biphenyls (PCBs) are a group of persistent organic pollutants consisting of 209 congeners. Oxidation of several PCB congeners to hydroxylated PCBs (OH-PCBs) in whole poplar plants has been reported before. Moreover, 2,2′,3,5′,6-pentachlorobiphenyl (PCB95), as a chiral congener, has been previously shown to be atropselectively taken up and transformed in whole poplar plants. The objective of this study was to determine if PCB95 is atropselectively metabolized to OH-PCBs in whole poplar plants. Two hydroxylated PCB95s were detected by high-performance liquid chromatography-mass spectrometry in the roots of whole poplar plants exposed to racemic PCB95 for 30 days. The major metabolite was confirmed to be 4′-hydroxy-2,2′,3,5′,6-pentachlorobiphenyl (4′-OH-PCB95) by gas chromatography-mass spectrometry (GC-MS) using an authentic reference standard. Enantioselective analysis showed that 4′-OH-PCB95 was formed atropselectively, with the atropisomer eluting second on the Nucleodex β-PM column (E2-4′-OH-PCB95) being slightly more abundant in the roots of whole poplar plants. Therefore, PCB95 can at least be metabolized into 4′-OH-PCB95 and another unknown hydroxylated PCB95 (as a minor metabolite) in whole poplar plants. Both atropisomers of 4′-OH-PCB95 are formed, but E2-4′-OH-PCB95 has greater atropisomeric enrichment in the roots of whole poplar plants. A comparison with mammalian biotransformation studies indicates a distinctively different metabolite profile of OH-PCB95 metabolites in whole poplar plants. Our observations suggest that biotransformation of chiral PCBs to OH-PCBs by plants may represent an important source of enantiomerically enriched OH-PCBs in the environment.     

Polychlorinated biphenyls and links to cardiovascular disease

The pathology of cardiovascular disease is multi-faceted, with links to many modifiable and non-modifiable risk factors. Epidemiological evidence now implicates exposure to persistent organic pollutants, such as polychlorinated biphenyls (PCBs), with an increased risk of developing diabetes, hypertension, and obesity; all of which are clinically relevant to the onset and progression of cardiovascular disease. PCBs exert their cardiovascular toxicity either directly or indirectly via multiple mechanisms, which are highly dependent on the type and concentration of PCBs present. However, many PCBs may modulate cellular signaling pathways leading to common detrimental outcomes including induction of chronic oxidative stress, inflammation, and endocrine disruption. With the abundance of potential toxic pollutants increasing globally, it is critical to identify sensible means of decreasing associated disease risks. Emerging evidence now implicates a protective role of lifestyle modifications such as increased exercise and/or nutritional modulation via anti-inflammatory foods, which may help to decrease the vascular toxicity of PCBs. This review will outline the current state of knowledge linking coplanar and non-coplanar PCBs to cardiovascular disease and describe the possible molecular mechanism of this association.     

Are the costs worth the benefits? Shared perception and the aggregation of organizational climate ratings

A definitional component of organizational climate is the focus on employees' shared perceptions of the focal climate domain. To operationalize the notion of sharedness, researchers typically aggregate employees' domain‐specific climate perceptions to a higher level and justify this aggregation using quantitative indices of agreement. In the current paper, I argue that although accounting for sharedness among employees can provide some valuable insight, our overreliance on sharedness obscures some of the very organizational phenomena of interest. I discuss this issue by focusing on four costs of making unfounded assumptions regarding sharedness: (a) Aggregation assumes individual differences are a function of random error; (b) aggregation assumes that social situations are uniform across employees; (c) aggregation assumes that the unit of analysis is clear‐cut; and (d) aggregation assumes the group mean is meaningful. I argue that researchers carefully need to weigh the costs of violating these assumptions against the expected benefits of aggregating employees' climate perceptions, recognizing that sometimes employees' perceptions (i.e., psychological climate) might provide greater insight into phenomena of interest. Although I discuss these costs within the context of organizational climate research, these arguments apply to other research areas where individual perceptions are aggregated (e.g., research on leadership and teams).     

Prioritizing sites for conservation based on similarity to historical baselines and feasibility of protection

The concept of shifting baselines in conservation science implies advocacy for the use of historical knowledge to inform these baselines but does not address the feasibility of restoring sites to those baselines. In many regions, conservation feasibility varies among sites due to differences in resource availability, statutory power, and land‐owner participation. We used zooarchaeological records to identify a historical baseline of the freshwater mussel community's composition before Euro‐American influence at a river‐reach scale (i.e., a kilometer stretch of river that is abiotically similar) in the Leon River of central Texas (U.S.A.). We evaluated how the community reference position and the feasibility of conservation might enable identification of sites where conservation actions would preserve historically representative communities and be likely to succeed. We devised a conceptual model that incorporated community information and landscape factors to link the best conservation areas to potential cost and conservation benefits. Using fuzzy ordination, we identified modern mussel beds that were most like the historical baseline. We then quantified housing density and land use near each river reach identified to estimate feasibility of habitat restoration. Using our conceptual framework, we identified reaches of high conservation value (i.e., contain the best mussel beds) and where restoration actions would be most likely to succeed. Reaches above Lake Belton were most similar in species composition and relative abundance to zooarchaeological sites. A subset of these mussel beds occurred in locations where conservation actions appeared most feasible. Our results show how to use zooarchaeological data (biodiversity data often readily available) and estimates of conservation feasibility to inform conservation priorities at a local spatial scale.     

Diminution of migration of phthalic acid esters in tequila beverage by the year of production

Abstract

The presence of diethyl-phthalate (DEP), dibutyl-phthalate (DBP), butylbenzyl-phthalate (BBP), diethylhexyl-phthalate (DEHP) and diisononyl-phthalate (DINP) was determined in 295 tequila samples. They were grouped by age of maturation (white, aged, extra aged or ultra aged) and year of production (between 2013 and 2018). Gas Chromatography coupled with Mass Spectrometry was used for identification and quantification. The results showed that 65 samples (22% of the total) were phthalate free. DEP (0.13-0.27?mg/kg), BBP (0.05–2.91?mg/kg) and DINP (1.64–3.43?mg/kg) were detected in 11 (3.73%), 37 (12.54%) and 5 (1.69%) samples, respectively. But, these concentrations did not exceed the maximum permitted limits (MPL) of phthalates for alcoholic beverages. DBP (0.01–2.20?mg/kg) and DEHP (0.03–4.64?mg/kg) were detected in 96 (32.54%) and 224 (75.93%) samples, from them only 10 (3.39%) and 15 (5.08%) samples, respectively, exceeded the MPL for alcoholic beverages and they were few tequilas produced in the year 2014 or before. DEHP was the most frequent phthalate found in tequila and observed DEHP concentrations were 2-times higher in ultra aged tequilas compared to those in white tequilas. We concluded that all tequilas produced in 2015 and after, satisfied the international standards for these compounds.     

Can we infer avalanche–climate relations using tree-ring data? Case studies in the French Alps

Dendrogeomorphology is a powerful tool to determine past avalanche activity, but whether or not the obtained annually resolved chronologies are sufficiently detailed to infer avalanche–climate relationships (in terms of temporal resolution) remains an open question. In this work, avalanche activity is reconstructed in five paths of the French Alps and crossed with a set of snow and weather variables covering the period 1959–2009 on a monthly and annual (winter) basis. The variables which best explain avalanche activity are highlighted with an original variable selection procedure implemented within a logistic regression framework. The same approach is used for historical chronologies available for the same paths, as well as for the composite tree-ring/historical chronologies. Results suggest that dendrogeomorphic time series allow capturing the relations between snow or climate and avalanche occurrences to a certain extent. Weak links exist with annually resolved snow and weather variables and the different avalanche chronologies. On the contrary, clear statistical relations exist between these and monthly resolved snow and weather variables. In detail, tree rings seem to preferentially record avalanches triggered during cold winter storms with heavy precipitation. Conversely, historical avalanche data seem to contain a majority of events that were released later in the season and during episodes of strong positive temperature anomalies.