Assessing exposure to transformation products of soil-applied organic contaminants in surface water: comparison of model predictions and field data

Transformation products (TPs) of chemicals released to soil, for example, pesticides, are regularly detected in surface and groundwater with some TPs even dominating observed pesticide levels. Given the large number of TPs potentially formed in the environment, straightforward prioritization methods based on available data and simple, evaluative models are required to identify TPs with a high aquatic exposure potential. While different such methods exist, none of them has so far been systematically evaluated against field data. Using a dynamic multimedia, multispecies model for TP prioritization, we compared the predicted relative surface water exposure potential of pesticides and their TPs with experimental data for 16 pesticides and 46 TPs measured in a small river draining a Swiss agricultural catchment. Twenty TPs were determined quantitatively using solid-phase extraction liquid chromatography mass spectrometry (SPE-LC-MS/MS), whereas the remaining 26 TPs could only be detected qualitatively because of the lack of analytical reference standards. Accordingly, the two sets of TPs were used for quantitative and qualitative model evaluation, respectively. Quantitative comparison of predicted with measured surface water exposure ratios for 20 pairs of TPs and parent pesticides indicated agreement within a factor of 10, except for chloridazon-desphenyl and chloridazon-methyl-desphenyl. The latter two TPs were found to be present in elevated concentrations during baseflow conditions and in groundwater samples across Switzerland, pointing toward high concentrations in exfiltrating groundwater. A simple leaching relationship was shown to qualitatively agree with the observed baseflow concentrations and to thus be useful in identifying TPs for which the simple prioritization model might underestimate actual surface water concentrations. Application of the model to the 26 qualitatively analyzed TPs showed that most of those TPs categorized as exhibiting a high aquatic exposure potential could be confirmed to be present in the majority of water samples investigated. On the basis of these results, we propose a generally applicable, model-based approach to identify those TPs of soil-applied organic contaminants that exhibit a high aquatic exposure potential to prioritize them for higher-tier, experimental investigations.     

Determination of cloud effective particle size from the multiple-scattering effect on lidar integration-method temperature measurements

A method is presented that permits the determination of the cloud effective particle size from Raman- or Rayleigh-integration temperature measurements that exploits the dependence of the multiple-scattering contributions to the lidar signals from heights above the cloud on the particle size of the cloud. Independent temperature information is needed for the determination of size. By use of Raman-integration temperatures, the technique is applied to cirrus measurements. The magnitude of the multiple-scattering effect and the above-cloud lidar signal strength limit the method's range of applicability to cirrus optical depths from 0.1 to 0.5. Our work implies that records of stratosphere temperature obtained with lidar may be affected by multiple scattering in clouds up to heights of 30 km and beyond.     

Mercury contamination in the vicinity of a derelict chlor-alkali plant Part II: contamination of the aquatic and terrestrial food chain and potential risks to the local population

This study investigated the environmental impact and level of risk associated with mercury (Hg) contamination near a derelict chlor-alkali plant in Pavlodar, Northern Kazakhstan. Several species of fish were sampled from the highly polluted Lake Balkyldak and the nearby river Irtysh, to assess the extent of Hg bioaccumulation in the aquatic food chain and potential human health risks. A small number of bovine tissue samples, water samples, soil and plant samples from a nearby village were also investigated in order to make a preliminary assessment of potential impacts on the terrestrial food chain. Mercury levels in fish caught from Lake Balkyldak ranged from 0.16 to 2.2 mg kg(-1) and the majority of fish exceeded current human health criteria for Hg. Interspecies comparisons indicated that Hg is accumulated in the order dace>carp>tench. Site-specific bioaccumulation factors (BAF) were calculated for THg, and were estimated for MeHg. Fish from the river Irtysh and floodplain oxbow lakes contained between 0.075 and 0.159 mg kg(-1) of Hg and can be regarded as uncontaminated. Soils were found to be impacted by past atmospheric emissions of Hg. Cattle grazing in the surroundings of the factory are exposed to Hg from contaminated soils, plants and surface water, but the consumption of contaminated fish from the lake appears to be the main route of exposure for humans.     

Vehicle Contribution to Ambient Carbonaceous Aerosols by Scaled Thermograms

Carbon thermograms, which classify carbon aerosol according to its volatility, were obtained for fine-particle samples from an isolated highway vehicle source and a vehicle-dominated ambient site. The thermograms from the sites were compared after scaling by the carbon monoxide concentration. The high- and low-volatility carbon fractions in the ambient sample agreed to within 10% of the corresponding fractions in the highway vehicle sample. Excess carbon in the range of intermediate volatility comprised 15 to 19% of the ambient carbon mass and is attributed to aerosols from secondary processes and nonvehicular primary sources. When lead was used as a tracer to scale the thermograms, the high- and low-volatility ambient carbon fractions were underestimated by a factor of 2. The low volatility fraction (“black carbon”) present in the atmospheric sample was evolved at lower temperatures than the equivalent fraction in the isolated highway vehicle sample. This creates an ambiguity in defining the low-volatility fraction, which is a problem if black carbon is used as a tracer. The scaling technique described in this work avoids the problem because it does not require an estimation of the low-volatility carbon fraction.     

Mercury contamination in the vicinity of a derelict chlor-alkali plant. Part I: sediment and water contamination of Lake Balkyldak and the River Irtysh

A mercury-cell chlor-alkali plant operated in Pavlodar, Northern Kazakhstan, for 18 years and caused widespread contamination of the surrounding environment. Untreated wastewater from the plant was discharged to Lake Balkyldak, a shallow impounded lake without an outlet. The nearby River Irtysh was also suspected to be impacted by mercury (Hg) via the transport of contaminated groundwater. We took sediment and water samples from both aquatic systems, and also sampled soils along the shoreline of the lake and in the Irtysh flood plain. Sediments from Lake Balkyldak were found to be very heavily contaminated, with Hg concentrations in the surface layer reaching up to approximately 1500 mg kg(-1) near the wastewater outfall pipe. The contaminated lake sediments are prone to wind-driven resuspension and are acting as a strong source of Hg to the water column. Unfiltered lake water samples taken in shallow areas within 10-15 m from the shoreline contained from 0.11 microg Hg L(-1) in the less contaminated northern part of the lake to 1.39 microg L(-1) near the pollutant outfall in the south (up to 7.3 microg L(-1) on windy days). Sediments from the River Irtysh were only slightly impacted, with maximum Hg concentrations of 0.046 mg kg(-1) in the old river channel and 0.36 mg kg(-1) in floodplain oxbow lakes. In water samples from the River Irtysh, Hg was generally not detected, although trace concentrations (3 to 9 ng L(-1)) were found in some samples taken from oxbow lakes. We conclude that the river is not significantly impacted by Hg, but the highly contaminated Lake Balkyldak poses a threat and is in need of remediation. Potential remediation options for the lake are reviewed and are discussed in the context of experiences made at other Hg-contaminated sites.     

Influence of fruit variety, harvest technique, quality sorting, and storage on the native microflora of unpasteurized apple cider

Apple variety, harvest, quality sorting, and storage practices were assessed to determine their impact on the microflora of unpasteurized cider. Seven apple varieties were harvested from the tree or the ground. The apples were used fresh or were stored at 0 to 4 degrees C for < or = 5 months and were pressed with or without quality selection. Cider yield, pH, Brix value, and titratable acidity were measured. Apples, postpressing apple pomace, and cider samples were analyzed for aerobic bacteria, yeasts, and molds. Aerobic bacterial plate counts (APCs) of ciders from fresh ground-picked apples (4.89 log CFU/ml) were higher than those of ciders made from fresh, tree-picked apples (3.45 log CFU/ml). Quality sorting further reduced the average APC to 2.88 log CFU/ml. Differences among all three treatment groups were significant (P < 0.0001). Apple and pomace microbial concentrations revealed harvest and postharvest treatment-dependent differences similar to those found in cider. There were significant differences in APC among apple varieties (P = 0.0001). Lower counts were associated with varieties exhibiting higher Brix values and higher titratable acidity. Differences in APC for stored and fresh apples used for cider production were not significant (P > 0.05). Yeast and mold counts revealed relationships similar to those for APCs. The relationship between initial microbial load found on incoming fruit and final cider microbial population was curvilinear, with the weakest correlations for the lowest apple microflora concentrations. The lack of linearity suggests that processing equipment contributed to cider contamination. Tree-picked quality fruit should be used for unpasteurized cider production, and careful manufacturing practices at cider plants can impact both safety and quality of the final product.     

Fibroblast Growth Factor 21 Response in a Preclinical Alcohol Model of Acute-on-Chronic Liver Injury

Background and Aims: Fibroblast growth factor (FGF) 21 has recently been shown to play a potential role in bile acid metabolism. We aimed to investigate the FGF21 response in an ethanol-induced acute-on-chronic liver injury (ACLI) model in Abcb4^−/− mice with deficiency of the hepatobiliary phospholipid transporter. Methods: Total RNA was extracted from wild-type (WT, C57BL/6J) and Abcb4⁻/⁻ (KO) mice, which were either fed a control diet (WT-Cont and KO-Cont groups; n = 28/group) or ethanol diet, followed by an acute ethanol binge (WT-EtOH and KO-EtOH groups; n = 28/group). A total of 58 human subjects were recruited into the study, including patients with alcohol-associated liver disease (AALD; n = 31) and healthy controls (n = 27). The hepatic and ileal expressions of genes involved in bile acid metabolism, plasma FGF levels, and bile acid and its precursors 7α- and 27-hydroxycholesterol (7α- and 27-OHC) concentrations were determined. Primary mouse hepatocytes were isolated for cell culture experiments. Results: Alcohol feeding significantly induced plasma FGF21 and decreased hepatic Cyp7a1 levels. Hepatic expression levels of Fibroblast growth factor receptor 1 (Fgfr1), Fgfr4, Farnesoid X-activated receptor (Fxr), and Small heterodimer partner (Shp) and plasma FGF15/FGF19 levels did not differ with alcohol challenge. Exogenous FGF21 treatment suppressed Cyp7a1 in a dose-dependent manner in vitro. AALD patients showed markedly higher FGF21 and lower 7α-OHC plasma levels while FGF19 did not differ. Conclusions: The simultaneous upregulation of FGF21 and downregulation of Cyp7a1 expressions upon chronic plus binge alcohol feeding together with the invariant plasma FGF15 and hepatic Shp and Fxr levels suggest the presence of a direct regulatory mechanism of FGF21 on bile acid homeostasis through inhibition of CYP7A1 by an FGF15-independent pathway in this ACLI model. Lay Summary: Alcohol challenge results in the upregulation of FGF21 and repression of Cyp7a1 expressions while circulating FGF15 and hepatic Shp and Fxr levels remain constant both in healthy and pre-injured livers, suggesting the presence of an alternative FGF15-independent regulatory mechanism of FGF21 on bile acid homeostasis through the inhibition of Cyp7a1.     

Regulation of Epigenetic Modifications in the Placenta during Preeclampsia: PPARγ Influences H3K4me3 and H3K9ac in Extravillous Trophoblast Cells

The aim of this study was to analyze the expression of peroxisome proliferator-activated receptor γ (PPARγ) and retinoid X receptor α (RxRα), a binding heterodimer playing a pivotal role in the successful trophoblast invasion, in the placental tissue of preeclamptic patients. Furthermore, we aimed to characterize a possible interaction between PPARγ and H3K4me3 (trimethylated lysine 4 of the histone H3), respectively H3K9ac (acetylated lysine 9 of the histone H3), to illuminate the role of histone modifications in a defective trophoblast invasion in preeclampsia (PE). Therefore, the expression of PPARγ and RxRα was analyzed in 26 PE and 25 control placentas by immunohistochemical peroxidase staining, as well as the co-expression with H3K4me3 and H3K9ac by double immunofluorescence staining. Further, the effect of a specific PPARγ-agonist (Ciglitazone) and PPARγ-antagonist (T0070907) on the histone modifications H3K9ac and H3K4me3 was analyzed in vitro. In PE placentas, we found a reduced expression of PPARγ and RxRα and a reduced co-expression with H3K4me3 and H3K9ac in the extravillous trophoblast (EVT). Furthermore, with the PPARγ-antagonist treated human villous trophoblast (HVT) cells and primary isolated EVT cells showed higher levels of the histone modification proteins whereas treatment with the PPARγ-agonist reduced respective histone modifications. Our results show that the stimulation of PPARγ-activity leads to a reduction of H3K4me3 and H3K9ac in trophoblast cells, but paradoxically decreases the nuclear PPARγ expression. As the importance of PPARγ, being involved in a successful trophoblast invasion has already been investigated, our results reveal a pathophysiologic connection between PPARγ and the epigenetic modulation via H3K4me3 and H3K9ac in PE.     

Different Narrow-Band Light Ranges Alter Plant Secondary Metabolism and Plant Defense Response to Aphids

Light of different wavelengths affects various physiological processes in plants. Short-wavelength radiation (like UV) can activate defense pathways in plants and enhance the biosynthesis of secondary metabolites (such as flavonoids and glucosinolates) responsible for resistance against certain herbivorous insects. The intensity of light-induced, metabolite-based resistance is plant- and insect species-specific and depends on herbivore feeding guild and specialization. In this study, broccoli (Brassica oleracea var. italica) plants were grown for 4 weeks in a climate chamber under conventional fluorescent tubes and were additionally treated with UV-B (310 nm), UV-A (365 or 385 nm), or violet (420 nm) light generated with UV-B tubes or light-emitting diodes (LEDs). The objective was to determine the influence of narrow bandwidths of light (from UV-B to violet) on plant secondary metabolism and on the performance of the cabbage aphid Brevicoryne brassicae (a specialist) and the green peach aphid Myzus persicae (a generalist). Among flavonol glycosides, specific quercetin and kaempferol glycosides increased markedly under UV-B, while among glucosinolates only 4-methoxy-3-indolylmethyl showed a 2-fold increase in plants exposed to UV-B and UV-A. The concentration of 3-indolylmethyl glucosinolate in broccoli plants increased with UV-B treatment. Brevicoryne brassicae adult weights and fecundity were lower on UV-B treated plants compared to UV-A or violet light-treated plants. Adult weights and fecundity of M. persicae were increased under UV-B and UV-A treatments. When specific light wavelengths are used to induce metabolic changes in plants, the specificity of the induced effects on herbivores should be considered.