Lipophilic Organic Compounds Research Articles

In vitro modeling of the post-ingestion mobilization and bioaccessibility of pesticides sorbed to soil and house dust

Soils and dusts can act as sinks for semivolatile lipophilic organic compounds and children ingest relatively large amounts of both soils and dusts. Following intake, sorbed chemicals may desorb (mobilize) and become available for intestinal absorption (bioaccessible). When chemicals are not degraded in the digestive tract, mobilization can approximate bioaccessibility. Alternatively, when gastrointestinal degradation of mobilized chemicals does occur, it can be useful to separate mobilization from bioaccessibility.In this study we used synthetic digestive fluids in a sequential, three-compartment (saliva, gastric, and intestinal) in vitro assay to construct mobilization and bioaccessibility models for 16 pesticides (log Kow 2.5–6.8) sorbed to 32 characterized soils and house dusts. To address the potential loss of mobilized pesticides due to absorption, the assays were repeated using a solid phase sorbent (tenax) added to the digestive fluid immediately after addition of the intestinal fluid components.We found that pesticide mobilization was predicted by pesticide log Kow and the carbon content of the soils and dusts. Pesticide loss measurably reduced the bioaccessibility of most pesticides, and bioaccessibility was largely predicted by log Kow and pesticide loss rate constants. Introduction of the sink increased mobilization by x̄ = 4 ± 6% (soil) and x̄ = 9 ± 7% (dust) while bioaccessibility increases were x̄ = 41 ± 21% (soil) and x̄ = 24 ± 12% (dust).The physicochemical properties of the soils, dusts, and pesticides used in this study successfully predicted the in vitro mobilization and bioaccessibility of the pesticides. This suggests that modeling of pesticide mobilization and bioaccessibility could reduce uncertainty in exposure and risk assessments.

Determination of Persistent Organic Pollutants in Human Breast Milk and Their Health Effects

Breast milk, the primary source of nutrition for infants, contains the ideal combination of carbohydrates, lipids, and proteins, and provides immunological and other health benefits that protect against infections. Persistent Organic Pollutants (POPs) are lipophilic organic compounds that accumulate in adipose tissue after being assimilated by the mother from the environment. Infants can be exposed to POP through breast milk, making breastfeeding a significant source of exposure. This review aims to provide a comprehensive overview of the numerous POPs that are contaminated in breast milk, the analytical techniques used to detect them in breast milk, and the potential health impacts of these pollutants on mothers through bioaccumulation and on infants through breastfeeding. Peer-reviewed articles published between 1989 and 2023 that covered several key features, including methodologies, health consequences, and other significant factors, were abstracted to assess the major results and research gaps. The majority of research investigated the relationship between POP concentrations in breast milk and socio-demographic variables. The studies revealed that several Organochlorine Pesticides (OCPs), Polychlorinated Biphenyls (PCBs), and their derivatives and industrial by-products such as polyaromatic hydrocarbons (PAHs) can contaminate breast milk, posing potential health risks to infants exposed to POPs through breast milk in many regions of the world.

PPARG is a potential target of Tanshinone IIA in prostate cancer treatment: a combination study of molecular docking and dynamic simulation based on transcriptomic bioinformatics

Tanshinone IIA is a lipophilic organic compound from the root of Danshen (Salvia miltiorrhiza) and is one of the most well-known Tanshinone molecules by pharmacologists. In recent years, in addition to effects of anti-cardiovascular and neurological diseases, Tanshinone IIA has also shown some degrees of anti-prostate cancer potential. Although they do have some studies focusing on the molecular mechanism of Tanshinone IIA’s anti-prostate cancer effects, a further understanding on the transcriptomic and structural level is still lacking. In this study, transcriptomic sequencing technology and computer technology were employed to illustrate the effects of Tanshinone IIA on prostate cancer through bioinformatic analysis and molecular dynamics simulation, and PPARG was considered to be one of the targets for Tanshinone IIA according to docking scoring and dynamic calculation. Our study provides a novel direction to further understand the mechanism of the effects of Tanshinone IIA on prostate cancer, and further molecular biological studies need to be carried on to further investigate the molecular mechanism of Tanshinone IIA’s anti-prostate cancer effect through PPARG.

Lymnaea stagnalis and Ophryotrocha diadema as Model Organisms for Studying Genotoxicological and Physiological Effects of Benzophenone-3.

Benzophenone-3 (BP-3) is a lipophilic organic compound that occurs naturally in flower pigments. Since it adsorbs ultraviolet (UV) radiation in the UVA and UVB regions, it is one of the most common UV filters found in sunscreen and cosmetic products. We explored by in vivo micronuclei (MNi) assay the genotoxic effects of BP-3 on hemocytes from the freshwater gastropod Lymnaea stagnalis. We also studied its possible toxic effects on life-history traits: body growth in L. stagnalis and egg production of both L. stagnalis and the marine polychaete worm Ophryotrocha diadema. Adult individuals were exposed to increasing concentrations of BP-3 (0.025, 0.050, 0.100, and 0.200 mg/L) once a week for 4 weeks. In L. stagnalis, exposure to BP-3 at concentrations of both 0.2 and 0.1 mg/L produced genotoxic effects on the micronuclei frequencies, but only concentrations of 0.2 mg/L affected the NBUDs frequencies. Similarly, negative effects on body growth were observed at the concentrations of 0.2 and 0.1 mg/L and a significant reduction of egg production at 0.2 mg/L. In O. diadema, a negative correlation between egg production and increasing BP-3 concentrations was observed. Our findings suggest the need for more stringent measures to reduce the presence of BP-3 in the environment.

Affecting Casein Micelles by Pulsed Electrical Field (PEF) for Inclusion of Lipophilic Organic Compounds

The increased consumption of reduced-fat or non-fat products leads to a reduced intake of fat-soluble bioactive substances, such as fat-soluble vitamins. Due to their natural role as transport systems for hydrophobic substances, casein micelles (CM) might depict a viable system. The structure of CM is characterized by a lipophilic core stabilized by an electric double layer-like structure. Modification allows accessibility of the core and, therefore, the inclusion of fat-soluble bioactive substances. Well-known modifications are pH reduction and use of rennet enzyme. A completely new procedure to modify CM structure is offered by pulsed electrical fields (PEF). The principle behind PEF is called electroporation and affects the electric double layer of CM so that it is interrupted. In this way, lipophilic substances can be incorporated into CM. In this work, we evaluated integration of β-carotene into native CM by an industry-compatible process to overcome disadvantages associated with the use of Na-caseinate and avoid great technical effort, e.g., due to treatment with high hydrostatic pressure. Our research has shown that PEF can be used for disintegration of CM and that significant amounts of β-carotene can be incorporated in CM. Furthermore, after disintegration using PEF, a combination of another PEF and thermal treatment was applied to restructure CM and trap significant amounts of β-carotene, permanently, ending up with an encapsulation efficiency of 78%.

PFAS Exposure Pathways for Humans and Wildlife: A Synthesis of Current Knowledge and Key Gaps in Understanding.

We synthesize current understanding of the magnitudes and methods for assessing human and wildlife exposures to poly- and perfluoroalkyl substances (PFAS). Most human exposure assessments have focused on 2 to 5 legacy PFAS, and wildlife assessments are typically limited to targeted PFAS (up to ~30 substances). However, shifts in chemical production are occurring rapidly, and targeted methods for detecting PFAS have not kept pace with these changes. Total fluorine measurements complemented by suspect screening using high-resolution mass spectrometry are thus emerging as essential tools for PFAS exposure assessment. Such methods enable researchers to better understand contributions from precursor compounds that degrade into terminal perfluoroalkyl acids. Available data suggest that diet is the major human exposure pathway for some PFAS, but there is large variability across populations and PFAS compounds. Additional data on total fluorine in exposure media and the fraction of unidentified organofluorine are needed. Drinking water has been established as the major exposure source in contaminated communities. As water supplies are remediated, for the general population, exposures from dust, personal care products, indoor environments, and other sources may be more important. A major challenge for exposure assessments is the lack of statistically representative population surveys. For wildlife, bioaccumulation processes differ substantially between PFAS and neutral lipophilic organic compounds, prompting a reevaluation of traditional bioaccumulation metrics. There is evidence that both phospholipids and proteins are important for the tissue partitioning and accumulation of PFAS. New mechanistic models for PFAS bioaccumulation are being developed that will assist in wildlife risk evaluations. Environ Toxicol Chem 2021;40:631-657. © 2020 SETAC.

The effect of the smoking process on polycyclic aromatic hydrocarbons contents in Hashemi and Domsiah rice cultivars

Polycyclic aromatic hydrocarbons (PAHs) are a group of lipophilic organic compounds consisting of two or more fused aromatic rings. Ingestion through contaminated food and water is a major route of human exposure to PAHs. Smoked products are important sources of dietary PAHs. Therefore, this study evaluated the effect of smoking times on the content of PAH compounds. The result showed that smoking duration had a significant effect on Benzo[a]pyrene (BaP) and 4PAH indices in both cultivars (Hashemi and Domsiah) between the three test groups (nonsmoked rice, rice smoked for 10 and 14 days) (p < .05). The level of BaP index in nonsmoked rice samples was lower than the permitted limit (1 μg/kg), but increased after smoking and exceeded the permitted limit. The 4PAH index was too high in both nonsmoked and smoked rice samples and the smoking process increased further. Finally, the smoking process had a significant direct effect on PAH compounds in Hashemi and Domsiah rice during the 14 days after smoking. Practical applications The polycyclic aromatic compounds have been identified as toxic compounds in most smoked food products such as meat, rice, and fish. The staple food of most people in the Middle East is rice, whose smoked form is mostly consumed. This source contains high amounts of polycyclic aromatic hydrocarbons. It is almost impossible to accurately measure them by traditional methods. The combination of the ultrasound-assisted extraction method and high-performance liquid chromatography with a fluorescence detection (HPLC/FLD) device can be a great help in accurately identifying these compounds in two varieties of smoked rice. Since most smoked rice workshops were traditionally built and operated, combustion conditions were usually not controlled properly and control criteria were not considered; therefore, smoked rice with high amounts of PAH compounds was produced. There is a need for replacement of the traditional smoking process with the industrial smoking process, use wood instead of paddy, revise the rice standard, and establish control limits for PAH compounds, especially for smoked rice.

Integrated Assessment of Bioconcentration, Toxicity, and Hazards of Chlorobenzenes in the Aquatic Environment.

The evaluation of bioconcentration, toxicity, and hazard (BTH) of persistent lipophilic organic compounds (LOCs) are generally performed as separate rather than integrated assessments. There are adequate data sets in the literature for chlorobenzenes (CBs) consisting of (a) concentrations in aquatic biota (CB) and water (Cw) in the natural environment, (b) laboratory-derived bioconcentration factors (KB) and field concentration ratios (CR), the field equivalent factor of KB, (c) measured internal lethal concentrations (ILC50) and model estimated ILC50 calculated from KB and lethal concentrations (LC50), and (d) calculated hazard quotients in aquatic biota (HQB) and in water (HQW). However, there have been no integrated studies of those parameter values based on the respective lipid-based parameters (CBL, KBL, CRL, ILC50L, HQBL) performed. This study utilized the lipid-based parameters for CBs; a group of widely occuring, bioaccumulative, and toxic LOCs, and integrated those parameters into a bioconcentration-toxicity-hazard (BTHL) index. The values of the parameters were obtained from selected literature with known lipid contents of the aquatic biota. The results showed that the laboratory derived bioconcentration factors, KBLs, were comparable to the corresponding field based factors, CRLs, and the measured internal lethal concentrations, ILC50L, showed comparable values with the estimated ones. The integrated BTHL index was less than an order of magnitude or moderately acceptable for the assessment of variability, uncertainty, and predictive power of the index. This integrated assessment can be used to support decision making dealing with CBs in specific and LOCs in general, both in regional and global aquatic environments.

Four Decades of Organic Anthropogenic Pollution: a Compilation for Djerdap Lake Sediments, Serbia

Analysis of limnic sediments can serve as a tool to assess sedimentary pollution for both the status quo as well as changes over time. However, in environmental studies, often only a small number of established well-studied contaminants are considered. This study focused on a more comprehensive investigation of sedimentary pollution of Djerdap Reservoir. Therefore, complementary analytical approaches were applied covering lipophilic organic contaminants and heavy metals. Investigations were performed on limnic sediment layers representing a period of 43 years of reservoir functioning. The core was sectioned on 11 samples and analyzed for, loss on ignition (LOI), and organic compounds (gas chromatography-mass spectrometry). Here, we report the quantitative data of 43 lipophilic organic compounds indicating both domestic and industrial emissions. Measured concentrations are generally low. Surprisingly, no polychlorinated biphenyls have been detected. Data concerning grain size, sedimentological, and inorganic composition were measured and published by in Kasanin-Grubin et al. (Kasanin-Grubin et al. 2019).

Isolation and characterization of two Acinetobacter species able to degrade 3-methylindole.

3-Methylindole (3MI) or Skatole is a volatile lipophilic organic compound produced by anoxic metabolism of L-tryptophan and associated with animal farming and industrial processing wastes. Pure cultures of bacteria capable of utilizing 3MI were isolated from chicken manure using enrichment culture techniques. The bacteria were identified as Acinetobacter toweneri NTA1-2A and Acinetobacter guillouiae TAT1-6A, based on 16S rDNA gene amplicon sequence data. The optimal temperature and pH for degradation of 3MI were established using single factor experiments. Strain tolerance was assessed over a range of initial concentrations of 3MI, and the effects of initial concentration on subsequent microbial 3MI degradation were also measured. During the degradation experiment, concentrations of 3MI were quantified by reverse-phase high-performance liquid chromatography (HPLC). The strains were capable of degrade initial concentrations of 3MI ranging from 65–200 mg/L. The degradation efficiency was >85% in 6 days for both strains when the initial concentration is less than 200 mg/L. The strains were tested for enzymatic activity using 65 mg/L 3MI. The enzyme extracts of NTA1-2A and TAT1-6A from the 3MI medium degraded 71.46% and 60.71% of 3MI respectively, but no appreciable change in 3MI concentration in the control group was witnessed. Our experiment revealed betaine and choline were identified as 3MI degradation metabolites by both strains while nitroso-pyrrolidine and beta-alaninebetaine formed by NTA1-2A and TAT1-6A strains respectively. The NTA1-2A and TAT1-6A strains removed 84.32% and 81.39% 3MI respectively from chicken manure during fermentation in 8 days and showed a statistically significant difference (P < 0.05) compared with the control group. The optimum temperature and pH were 31°C and 6 respectively, for 3MI degradation by A. toweneri NTA1-2A and A. guillouiae TAT1-6A. We concluded that A. toweneri NTA1-2A and A. guillouiae TAT1-6A are potential strains of interest to degrade 3MI and control odorant in poultry and other livestock industries.

Simultaneous Electrochemical Determination of Vitamin K1 and Vitamin D3 by using Poly (Alizarin Red S)/Multi-walled Carbon Nanotubes Modified Glassy Electrode

Background: The goal of this research is to develop a new electroanalytical procedure for the simultaneous electrochemical detection of vitamin K1 (VK1) and vitamin D3 (VD3), in a sodium dodecyl sulfate (SDS) -containing buffer solution, with no detectable interference of other kinds of vitamin A and vitamin E present in the sample solution. Surfactant solutions are well known their capability to dissolve oil-soluble substance such as dyes, hydrocarbons, esters, perfumes, and so on. Micellar solubilization is the powerful alternative for the dissolution of poorly soluble or hydrophobic compounds in aqueous environments. Surfactants micellar media can be successfully applied for the solubilization of lipophilic organic compounds in water media and enhancement of their electrochemical activity. In this research, the anionic surfactant SDS was used as the solubilizing agent. Keywords: Vitamin K1, vitamin D3, simultaneous determination, voltammetry, alizarin red S, carbon nanotube, food analysis.

Circumpolar contaminant concentrations in polar bears (Ursus maritimus) and potential population-level effects

Polar bears (Ursus maritimus) currently receive much attention in the context of global climate change. However, there are other stressors that might threaten the viability of polar bear populations as well, such as exposure to anthropogenic pollutants. Lipophilic organic compounds bio-accumulate and bio-magnify in the food chain, leading to high concentrations at the level of top-predators. In Arctic wildlife, including the polar bear, various adverse health effects have been related to internal concentrations of commercially used anthropogenic chemicals like PCB and DDT. The extent to which these individual health effects are associated to population-level effects is, however, unknown. In this study we assembled data on adipose tissue concentrations of ∑PCB, ∑DDT, dieldrin and ∑PBDE in individual polar bears from peer-reviewed scientific literature. Data were available for 14 out of the 19 subpopulations. We found that internal concentrations of these contaminants exceed threshold values for adverse individual health effects in several subpopulations. In an exploratory regression analysis we identified a clear negative correlation between polar bear population density and sub-population specific contaminant concentrations in adipose tissue. The results suggest that adverse health effects of contaminants in individual polar bears may scale up to population-level consequences. Our study highlights the need to consider contaminant exposure along with other threats in polar bear population viability analyses.

Pine needles and pollen grains of Pinus mugo Turra – A biomonitoring tool in high mountain habitats identifying environmental contamination

Pinus mugo Turra is a typical pine tree from mountain habitats. It is ideal as a bioindicator for air quality monitoring, but, to the best of our knowledge, has never been implemented to determine organic compound concentrations. This study presents the initial methodology for the use of pine needles to measure contamination levels and evaluate genotoxicity potentials caused by long-range transport of pollutants at sites in the Slovak mountains in comparison to an industrial urban area. Pinus mugo needles have many positive attributes, particularly the five-year lifetime of needles compared with other species of pine. The presence of epicuticular wax on the surface of needles allows accumulation of lipophilic organic compounds. Pine needles were analyzed for POP compounds (PCBs, OCPs, PBDEs), PAHs, PFCs and lead. A pollen grain abortion assay with Pinus mugo species was also tested as a method to identify contamination of high mountain habitats. The concentration of organic compounds increased proportionally with needle age. Concentrations along the mountain transect were heavily influenced by atmospheric transport and proximity to potential sources of contamination from industry and residential areas from north and south of the mountain. The slope exposure direction had a large impact on concentrations of PBDEs (mainly for BDE 209). High concentrations of PFCs were discovered near a ski resort, where the use of these substances is high due to fluorinated ski waxes and personal outdoor clothing. A positive correlation between pollen grain abortivity and elevation was observed, with the strongest effect on pollutants at the top of the mountains. The results showed the highest genotoxicity at the site near a pulp mill (Zilina), where the frequency of abortive pollen grains was 3.1 times higher than at the control site. Lead content increased gradually with needle age, and a correlation was found between Pb levels in needles and pollen abortivity. It can be concluded that Pinus mugo is a suitable bioindicator species for assessment of long-term trends of atmospheric contamination in high mountain habitats.

Effects of exercise and temperature on geosmin excretion by European eel (Anguilla anguilla)

The presence of geosmin in fish products causes an earthy or musty off-flavour. To avoid economic damage resulting from market entrance of off-flavoured fish products, fish farmers utilize the reversibility of geosmin uptake to depurate the off-flavours from their fish crops by holding them in clean water just before harvest. To improve this process, effects of exercise and temperature on the excretion of geosmin by European eel (Anguilla anguilla) were assessed. Fish loaded with geosmin were depurated for 23h during which they were subjected to combinations of exercise (spontaneous swimming activity at 0.05ms−1 or forced swimming at optimal swimming speed of 0.55ms−1) and temperature (15°C or 25°C) treatments. Oxygen consumption was measured during depuration. Whole body geosmin concentrations were measured in samples collected at t=0 and t=23h to assess geosmin excretion. Geosmin excretion by European eel was clearly enhanced by exercise, but temperature had no statistically significant effect. Exercise increased oxygen consumption, which in turn showed a positive linear relation with geosmin excretion. These findings support the idea that the physiological responses aimed at increasing oxygen uptake also affect the branchial exchange of lipophilic xenobiotic chemicals between the fish and its surroundings. Exercise can be used to reduce the time required to depurate off-flavours from fish. These findings are relevant for aquaculture industries confronted with off-flavoured fish crops. Statement of relevanceFish raised in land-based aquaculture systems may bio-concentrate geosmin, a lipophilic organic compound produced by microbiota. The presence of geosmin in fish products causes an earthy or musty off-flavour which human consumers do not appreciate and this poses one of the most significant economic problems for land-based aquaculture. To avoid economic damage resulting from market entrance of off-flavoured fish, fish farmers utilize the reversibility of geosmin bio-concentration to depurate the off-flavours from their fish crops. To this end fish are kept in water free of geosmin just before harvest. This procedure, however, is not always sufficiently effective and it is costly as it requires time, effort and use of specific facilities. Therefore better understanding of factors enhancing the geosmin excretion is needed to be able to improve the off-flavour depuration process. This study established that forced exercise during off-flavour depuration increases the rate at which European eel eliminates geosmin from its body. Forcing fish to swim during off-flavour depuration shortens the required depuration time. This finding is relevant for the aquaculture industries confronted with off-flavoured fish crops.

Body Mass Parameters, Lipid Profiles and Protein Contents of Zebrafish Embryos and Effects of 2,4-Dinitrophenol Exposure.

Morphology and physiology of fish embryos undergo dramatic changes during their development until the onset of feeding, supplied only by endogenous yolk reserves. For obtaining an insight how these restructuring processes are reflected by body mass related parameters, dry weights (dw), contents of the elements carbon and nitrogen and lipid and protein levels were quantified in different stages within the first four days of embryo development of the zebrafish (Danio rerio). The data show age dependent changes in tissue composition. Dry weights decreased significantly from 79μgdw/egg at 0hours post fertilization (hpf) to 61 μgdw/egg after 96 hpf. The amounts of total carbon fluctuated between 460 mg g-1 and 540 mg g-1 dw, nitrogen was at about 100 mg g-1 dw and total fatty acids were between 48–73 mg g-1 dw. In contrast to these parameters that remained relatively constant, the protein content, which was 240 mg g-1 at 0 hpf, showed an overall increase of about 40%. Comparisons of intact eggs and dechorionated embryos at stages prior to hatching (24, 30, 48 hpf) showed that the differences seen for dry weight and for carbon and nitrogen contents became smaller at more advanced stages, consistent with transition of material from the chorion to embryo tissue. Further, we determined the effect of 2,4-dinitrophenol at a subacutely toxic concentration (14 μM, LC10) as a model chemical challenge on the examined body mass related parameters. The compound caused significant decreases in phospholipid and glycolipid fatty acid contents along with a decrease in the phospholipid fatty acid unsaturation index. No major changes were observed for the other examined parameters. Lipidomic studies as performed here may thus be useful for determining subacute effects of lipophilic organic compounds on lipid metabolism and on cellular membranes of zebrafish embryos.

Phytoremediation mechanisms for polycyclic aromatic hydrocarbons removing from contaminated soils

Phytoremediation of polycyclic aromatic hydrocarbons (PAHs) from soil aims to degrade them into less toxic/non toxic compounds and limit their further movement by sequestration and accumulation into the vacuoles. Lipophilic organic compounds such as PAHs are bound strongly to the epidermis of the root tissue and are rarely translocated within plant. There are no reports in the literature data of PAHs being completely mineralized by plants. There is little evidence to suggest that PAHs accumulate to significant degree in plants, but there still is a lot of evidences on the ability of various plant species (most often grasses and legumes), to degrade and dissipate these dangerous contaminants. The primary mechanism controlling the dissipation of PAHs is rhizosphere microbial degradation where microbes use PAHs molecules as carbon substrates for growth, which in final, leads to the breakdown or total mineralization of the contaminants. The process is usually augmented by the excretion of root exudates (e.g., sugars, alcohols, acids, enzymes), and the build-up of organic carbon in the soil, so the proper selection of particular plant species represents a critical management decision for PAHs phytoremediation. These facts favor the rhyzoremediation as the best solution for sites contaminated with PAHs.

Interaction of Carbon Nanomaterial Fullerene (C60) and Microcystin-LR in Gills of Fish Cyprinus carpio (Teleostei: Cyprinidae) Under the Incidence of Ultraviolet Radiation

One of the most widely used carbon nanomaterials is fullerene (C60), a lipophilic organic compound that potentially can behave as a carrier of toxic molecules, enhancing the entry of environmental contaminants in specific organs. Microcystins (MC) are cyanotoxins very toxic for human and environmental health. Several studies showed that exposure to MC or C60 generates reactive oxygen species (ROS) and changes in antioxidant levels. Also, another factor that can come to enhance the toxic potential of both MC and C60 is UVA radiation. Therefore, it was evaluated the effects on oxidative stress parameters of ex vivo co-exposure of MC and C60 (5 mg/l) in gills of the fish Cyprinus carpio under UVA radiation incidence. The results showed that (a) there was a loss of antioxidant capacity after low MC concentration (L, 50 μg/l) + C60 co-exposure under UVA, (b) C60 under UVA decreased glutathione-S-transferase (GST) activity, (c) high MC concentration (H, 200 μg/l) + C60 co-exposure decreased the concentrations of glutathione (GSH) under UVA or in the dark, (d) L under UVA increased lipid peroxidation, and (e) C60 did not cause a higher bioaccumulation of MC in gills. The lowering of GSH in H + C60 co-exposure should compromise MC detoxification mediated by GST, although toxin accumulation is not influenced by C60.

Biological activity of bleached kraft pulp mill effluents before and after activated sludge and ozone treatments

Eucalyptus bleached kraft pulp production, an important sector of the Brazilian national economy, is responsible for generating large volume, high pollutant load effluents, containing a considerable fraction of recalcitrant organic matter. The objectives of this study were to quantify the biological activity of the effluent from a eucalyptus bleached kraft pulp mill, characterize the nature of compounds responsible for biological activity and assess the effect of ozone treatment on its removal. Primary and secondary effluents were collected bimonthly over the course of one year at a Brazilian bleached eucalypt kraft pulp mill and their pollutant loads (biochemical oxygen demand (BOD), chemical oxygen demand (COD), total organic carbon (TOC), adsorbable organic halogen (AOX), lignin, extractives) and biological activity (acute and chronic toxicity and estrogenic activity) quantified. The effluent studied did not present acute toxicity to Daphnia, but presented the chronic toxicity effects of algal growth inhibition and reduced survival and reproduction in Ceriodaphnia, as well as estrogenic activity. Chronic toxicity and estrogenic activity were reduced but not eliminated during activated sludge biological treatment. The toxicity identification evaluation revealed that lipophilic organic compounds (such as residual lignin, extractives and their byproducts) were responsible for the toxicity and estrogenic activity. Ozone treatment (50 mg/L O(3)) of the secondary effluent eliminated the chronic toxicity and significantly reduced estrogen activity.

Preliminary evaluation of the persistence of organic gunshot residue

The organic components of gunshot residue (OGSR, also called firearms discharge residue (FDR) or cartridge discharge residue (CDR)) have been studied and discussed in the literature. These residues, consisting of particulates such as burned and unburned powder as well as molecular compounds, are rarely used in casework except for purposes such as shooting reconstructions. Molecular compounds that survive the firing event or that are created as a result of the firing event could, with focused research and development, open a new avenue for forensic gunshot residue analysis. In this study, the persistence of organic gunshot residue was evaluated using diphenylamine (DPA) as a target analyte and ion mobility spectrometry (IMS) as the detection system. Samples were collected from hands using a solvent swabbing technique and the swab was analyzed using direct thermal desorption for sample introduction into the IMS. OGSR was found to persist for at least 4h. Although DPA is a widely used industrial compound, analysis of numerous blank and background samples (n∼100) did not show any significant response for DPA using this detector. Variations were noted among individuals and as such, the data set does not support estimation of a half-life as has been done for traditional primer residues. No secondary transfers were observed, suggesting the possibility of skin adhesion via interactions between the lipophilic organic compounds and skin lipids. IMS proved valuable as a means of generating patterns for forensic pattern matching and shows promise as a screening tool applied to firearms discharge.

Effect of a Microemulsion System on Hapten-Peptide Reactivity Studies: Examples of Hydroxycitronellal and Citral, Fragrance Skin Sensitizers, with Glutathione

In chemico methods, based on the assessment of hapten reactivity toward peptides, have been proposed as alternative methods for the assessment of the skin sensitizing potential of chemicals. However, even if these approaches seem very promising, a major drawback inherent to most in vitro methods is the poor water solubility of many organic molecules in aqueous media. Thus, semiorganic media based on buffer solutions and organic cosolvents such as ethanol or acetonitrile have been proposed, but a narrow equilibrium should be found between the peptide and chemical solubilities. Microemulsions have been shown to be very valuable when reacting a lipophilic organic compound soluble in hydrophobic media with a very hydrophilic organic substance insoluble in most organic solvents. However, the reaction rate between polar and apolar reactants can be influenced, in some cases, by the use of microemulsions. On the basis of NMR experiments, we have compared the reactivity of hydroxycitronellal 1 and citral 2, two weak fragrance sensitizers of major clinical relevance, toward glutathione used as a model nucleophile in a water/acetonitrile 2:1 mixture and in a microemulsion based on chloroform/water/tert-butanol/sodium dodecylsulphate. Hydroxycitronellal and citral were found to react with the thiol group of glutathione to form, in both media, identical adducts, but the observed reaction rates were found to be different. In the case of hydroxycitronellal, the observed reaction rate of glutathione addition on the aldehyde was found to be about three times higher in the microemulsion compared to the classical semiorganic mixture. In the case of citral, the situation was more complex as the Michael addition of glutathione on the conjugated double bond was found to be significantly faster in the classical semiorganic mixture, while the subsequent reaction of a second glutathione molecule on the aldehyde was found to be faster in the microemulsion. This chloroform/water/tert-butanol/sodium dodecylsulphate microemulsion, apparently of the bicontinuous type according to DOSY data, could be of potential interest for the in chemico evaluation of lipophilic chemicals toward peptides to solve solubility problems even if the impact on the chemical rate needs to be further investigated.