Dioxins,chlorophenols and other chlorinated organic pollutants in colloidal and water fractions of groundwater from a contaminated sawmill site

BACKGROUND, AIM, AND SCOPE: The distribution of chlorinated organic contaminants in groundwater and the importance of colloids were studied in groundwater from a sawmill site contaminated by chlorophenol preservatives. MATERIALS AND METHODS: The groundwater was fractionated into three different size ranges: (1) >0.7 mum, (2) 0.4-0.7 mum and (3) 0.2-0.4 mum and the filtered water phase. The concentrations of chlorophenols (CP), chlorinated phenoxy phenols (PCPP), chlorinated diphenyl ethers (PCDE), chlorinated dibenzofurans (PCDF) and chlorinated dibenzo-p-dioxins (PCDD) were determined in each fraction. The colloids were characterised regarding the chemical composition using X-ray photoelectron spectroscopy (XPS). RESULTS: Chlorophenols were mostly found in the water fraction and PCDD/Fs were found almost exclusively in the particulate fractions. For example, the filtered water phase contained 2,100 mug l(-1) and 0.72 ng l(-1) for CPs and PCDD/Fs, respectively, and the particulate fractions contained 27 mug l(-1) and 32 ng l(-1) for CPs and PCDD/Fs, respectively. XPS evaluation of the particulate phases showed no correlation between the surface chemistry of the particle properties and the distribution of chlorinated compounds. DISCUSSION: The results suggest that groundwater transport of CPs, PCPPs, PCDEs and PCDD/Fs may occur from contaminated sawmill sites and that the colloid-facilitated transport, especially of PCDD/Fs, is substantial. The results correlated well with previous studies of compounds sorbed to dissolved organic carbon, which indicate that dissolved and colloidal organic carbon facilitated the transport of PCDEs, PCDFs and PCDDs particularly. CONCLUSIONS: Several classes of chlorinated compounds were readily detected in the groundwater samples. Due to the differences in their physicochemical properties, CPs, PCPPs, PCDEs and PCDD/Fs vary in their partitioning between colloidal fractions and the filtered groundwater. The proportion of the bound fraction increased with an increasing hydrophobicity of the chlorinated compounds. The groundwater transport of colloid-associated pollutants from the site may be significant. RECOMMENDATIONS AND PERSPECTIVES: The results imply that colloidal particles <0.7 mum are freely mobile in groundwater from this site. The groundwater transport of colloid-associated pollutants may be significant. However, the extent of the problem is not yet known and, thus, further research is needed to evaluate the impact of colloidal transport of hydrophobic organic contaminants. In Sweden alone, 400 to 500 sawmill sites are estimated to be contaminated with PCDD/Fs as a result of the former use of CP-based wood preservatives. The widespread use of CP mixtures for a variety of applications, including wood preservation, indicates that potential colloidal transport will be an issue of concern in many countries.     

Investigation of polyhydroxyalkanoates (PHAs) biosynthesis from mixed culture enriched by valerate-dominant hydrolysate

The production of polyhydroxyalkanoates (PHAs) with a high fraction of 3-hydroxyvalerate (3HV) and 3-hydroxy-2-methylvalerate (3H2MV) from mixed culture enriched by valerate-dominant hydrolysate was evaluated in this study. After long-term enrichment, the culture showed strong ability to synthesize 3HV and 3H2MV, even with acetate-dominant substrate. The ultilization of single or mixed iso-/n-valerate by the enriched culture showed that the mixture of iso-valerate and n-valerate was more efficient substrate than any single in terms of balancing microbial growth and PHAs synthesis. Besides, through comparing the kinetics and stoichiometry of the tests supplying valerate and propionate, the enriched culture with equivalent valerate and propionate (1:1 molar ratio) exhibited superior PHAs production performances to pure valerate or propionate, attaining more than 70 mol% of 3HVand 3H2MV. The above findings reveal that valerate-dominant hydrolysate is a kind of suitable substrate to enrich PHAs producing culture with great capability to synthesize 3HV and 3H2MV monomers, thus improving product properties than pure poly(3-hydroxybutyrate) (P3HB); also 3HV and 3H2MV production behaviors can be regulated by the type of odd-carbon VFAs in the substrate.

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Evaluation of geomorphic changes and retreat rates of a coastal pyroclastic cliff in the Campi Flegrei volcanic district,southern Italy

Geomorphic evolution of sea cliffs has significant impact on coastal settlements worldwide, so that evaluation of cliff instability processes, failure factors, and retreat rates involves a growing number of scientists for coastal risk and management purposes. Aerial photogrammetry and lidar are among the most used techniques for topographic characterization and geomorphic monitoring of coastal environments. A crucial role in the combined use of such techniques is the evaluation of different spatial accuracy and co-registration between derived terrain models, so that a robust error analysis is required. In this study, we present a change detection analysis of the Torrefumo coastal cliff, in the Campi Flegrei volcanic area (Southern Italy). Aerial images taken in 1956 and 1974, processed through digital photogrammetry, and an airborne lidar point cloud acquired in 2008 were used to produce Digital Elevation Models of the cliff. The analysis was based on the multi-temporal comparison of these models and included the calculation of volumetric changes and average retreat rates of the cliff face with reference to the 1956–1974 and 1974–2008 time intervals. The spatially variable elevation uncertainty of each Digital Elevation Model was evaluated with a probabilistic approach based on the fuzzy set theory. The results of this study showed significant eroded volumes during the period 1956–1974 and relatively smaller volumes in the 1974–2008 time span, with mean annual retreat rates of 1.2 m/year and 0.17 m/year, respectively. We infer that the significant decrease of erosion characterizing the second period was induced by the sheltering effect at the base of the cliff produced by the construction of a seawall in the early 80’s.     

Absorption characteristics of potassium carbonate-based solutions with rate promoters and corrosion inhibitors

In this research, absorbents for CO₂ capture were prepared by blending 30 wt% potassium carbonate, 3 wt% of a rate promoter, and 1 wt% of a corrosion inhibitor. Pipecolic acid, sarcosine, and diethanolamine were chosen as rate promoter candidates. Based on a rate promoter screening test for CO₂ loading capacity and absorption rate, pipecolic acid and sarcosine were selected to be used as rate promoters. 1,2,3-benzotriazole and ammonium thiocyanate were chosen as corrosion inhibitors, and they were mixed with a 30 wt% potassium carbonate-based absorbent mixture containing one of the rate promoters. The absorption rates for four absorbent solutions (30 wt% potassium carbonate?+?3 wt% pipecolic acid?+?1 wt% 1,2,3-benzotriazole, 30 wt% potassium carbonate?+?3 wt% pipecolic acid?+?1 wt% ammonium thiocyanate, 30 wt% potassium carbonate?+?3 wt% sarcosine?+?1 wt% 1,2,3-benzotriazole, and 30 wt% potassium carbonate?+?3 wt% sarcosine?+?1 wt% ammonium thiocyanate) were measured, tabulated, and graphically displayed. These types of absorbents can be used for capturing CO₂ under high temperature and pressure conditions, such as those found in coal-fired power plants.     

Ethoxylated Soybean Polyols for Polyurethanes

Soybean polyols prepared by ring opening reactions of epoxidized soybean oil with hydrogen active compounds (water, alcohols, organic or inorganic acids, thiols, hydrogen etc.) have a low reactivity in the reaction with isocyanates because the hydroxyl groups are secondary. This paper presents a simple and convenient method to increase the reactivity of soybean polyols with secondary hydroxyl groups by ethoxylation reactions with the preservation of triglyceride ester bonds. The method uses mild reaction conditions: low alkoxylation temperature of 35–45 °C, low pressure of 0.1–0.2 MPa (15–30 p.s.i.) and a superacid as catalyst (HBF₄). The new soybean polyols have a higher reactivity toward isocyanates in polyurethane formation due to the high percentage of primary hydroxyl groups. The primary hydroxyl content was determined by the second order kinetics of polyol reaction with phenyl isocyanate.     

Re-construction of the shut-down PM10 monitoring stations for the reliable assessment of PM10 in Berlin using fuzzy modelling and data transformation

A dense monitoring network is vital for the reliable assessment of PM10 in different parts of an urban area. In this study, a new idea is employed for the re-construction of the 20 shut-down PM10 monitoring stations of Berlin. It endeavours to find the non-linear relationship between the hourly PM10 concentration of both the still operating and the shut-down PM10 monitoring stations by using a fuzzy modelling technique, called modified active learning method (MALM). In addition, the simulations were performed by using not only raw PM10 databases but also log-transformed PM10 databases for skewness reduction. According to the results of hourly PM10 simulation (root mean square error about 13.0 μg/m³, correlation coefficient 0.88), the shut-down stations have been appropriately simulated and the idea of dense monitoring network development by the re-construction of the shut-down stations was realised. The results of simulations using raw and log-transformed databases showed that data transformation has no significant effect on the performance of MALM in the simulation of shut-down PM10 stations. By the combination of the 11 still operating stations and the 20 re-constructed stations, a dense monitoring network was generated for Berlin and was utilised for the calculation of the reliable monthly and mean annual PM10 concentration for five different PM10 zones in Berlin (the suburban-background, urban-background, urban-traffic, rural-background and suburban-traffic areas). The results showed that the mean annual concentration of PM10 at the five zones increased by about 13.0% in 2014 (26.3 μg/m³) in comparison with 2013 (23.3 μg/m³). Furthermore, the mean annual concentration of PM10 in the traffic lanes of the suburban (2013 25.0 μg/m³, 2014 26.9 μg/m³) and urban (2013 27.7 μg/m³, 2014 31.3 μg/m³) areas is about 14 and 20% higher than the PM10 concentration of suburban-background (2013 21.3 μg/m³, 2014 24.5 μg/m³) and urban-background (2013 23.0 μg/m³, 2014 26.1 μg/m³) areas, respectively.     

Comparison of Hydrology of Wetlands in Pennsylvania and Oregon (USA) as an Indicator of Transferability of Hydrogeomorphic (HGM) Functional Models Between Regions

The hydrogeomorphic (HGM) approach to wetland classification and functional assessment is becoming more widespread in the United States but its use has been limited by the length of time needed to develop appropriate data sets and functional assessment models. One particularly difficult aspect is the transferability among geographic regions of specific models used to assess wetland function. Sharing of models could considerably shorten development and implementation of HGM throughout the United States and elsewhere. As hydrology is the driving force behind wetland functions, we assessed the comparability of hydrologic characteristics of three HGM subclasses (slope, headwater floodplain, mainstem floodplain) using comparable long-term hydrologic data sets from different regions of the United States (Ridge and Valley Province in Pennsylvania and the Willamette Valley in Oregon). If hydrology by HGM subclass were similar between different geographic regions, it might be possible to more readily transfer extant models between those regions. We found that slope wetlands (typically groundwater-driven) had similar hydrologic characteristics, even though absolute details (such as depth of water) differed. We did not find the floodplain subclasses to be comparable, likely due to effects of urbanization in Oregon, regional differences in soils and, perhaps, climate. Slight differences in hydrology can shift wetland functions from those mediated by aerobic processes to those dominated by anaerobic processes. Functions such as nutrient cycling can be noticeably altered as a result. Our data suggest considerable caution in the application of models outside of the region for which they were developed.     

DNA Heat Treatment for Improving qPCR Analysis of Human Adenovirus in Wastewater

PCR inhibitory substances in complex sample matrices can cause false negatives or under-estimation of target concentration. This study assessed DNA heat treatment for reducing inhibition during qPCR analysis of human adenovirus (HAdV) in wastewater samples. Inhibition was reduced by heat treating DNA, where mean HAdV concentration was increased by 0.71 log₁₀ GC/L (and up to 3.04 log₁₀ GC/L in one case), and replicate variability and false negatives were reduced. DNA heat treatment should be further investigated for improving reliability of HAdV concentration estimates in water, which can support more accurate assessment of health risks associated with viral pathogen exposure.