Monitoring OH-PCBs in PCB transport worker’s urine as a non-invasive exposure assessment tool

In this study, we analyzed hydroxylated polychlorinated biphenyls (OH-PCBs) in urine of both PCB transport workers and PCB researchers. A method to monitor OH-PCB in urine was developed. Urine was solid-phase extracted with 0.1% ammonia/ methanol (v/v) and glucuronic acid/sulfate conjugates and then decomposed using β-glucuronidase/arylsulfatase. After alkaline digestion/derivatization, the concentration of OH-PCBs was determined by HRGC/HRMS-SIM. In the first sampling campaign, the worker’s OH-PCB levels increased several fold after the PCB waste transportation work, indicating exposure to PCBs. The concentration of OH-PCBs in PCB transport workers’ urine (0.55~11 μg/g creatinine (Cre)) was higher than in PCB researchers’ urine (< 0.20 μg/g Cre). However, also a slight increase of OH-PCBs was observed in the researchers doing the air sampling at PCB storage area. In the second sampling, after recommended PCB exposure reduction measures had been enacted, the worker’s PCB levels did not increase during handling of PCB equipment. This suggests that applied safety measures improved the situation. Hydroxylated trichlorobiphenyls (OH-TrCBs) were identified as a major homolog of OH-PCBs in urine. Also, hydroxylated tetrachlorobiphenyls (OH-TeCBs) to hydroxylated hexachlorobiphenyls (OH-HxCBs) were detected. For the sum of ten selected major indicators, a strong correlation to total OH-PCBs were found and these can possibly be used as non-invasive biomarkers of PCB exposure in workers managing PCB capacitors and transformer oils. We suggest that monitoring of OH-PCBs in PCB management projects could be considered a non-invasive way to detect exposure. It could also be used as a tool to assess and improve PCB management. This is highly relevant considering the fact that in the next 10 years, approx. 14 million tons of PCB waste need to be managed. Also, the selected populations could be screened to assess whether exposure at work, school, or home has taken place.     

Mapping the global supply and demand structure of rice

Rice plays a major role in the global supply and demand for sustainable food production. The constraints of maintaining sustainable rice production are closely linked to the relationship between the distribution patterns of human activity on the planet and economic growth. Global patterns of rice production can be mapped by using various criteria linked to domestic income, population patterns, and associated satellite brightness data of rice-producing regions. Prosperous regions have more electric lighting, and there are documented correlations between gross domestic product (GDP) and nighttime light. We chose to examine global rice production patterns on a geographical basis. For the purposes of this study, each country is considered to be made up of regions, and rice production is discussed in terms of regional distribution. A region is delineated by its administrative boundaries; the number of regions where rice is produced is about 13,839. We used gridded spatial population distribution data overlain by nocturnal light imagery derived from satellite imagery. The resultant relationship revealed a correlation between regional income (nominal values of GDP were used) and rice production in the world. The following criteria were used to examine the supply and demand structure of rice. Global rice consumption = “caloric rice consumption per capita per day” multiplied by “regional population values”. Regional rice yields = “country-based production” divided by “harvested area” (multiple harvests are taken into account). Regional rice production = “regional harvested areas” multiplied by “rice yield values”. We compared regional rice consumption and production values according to these methods. Analysis of the data sets generated a map of rice supply and demand. Inter-regional shipping costs were not accounted for. This map can contribute to the understanding of food security issues in rice-producing regions and to estimating potential population values in such regions.     

Characterization of the pattern of the nongenomic signaling pathway through which TCDD-induces early inflammatory responses in U937 human macrophages

2,3,7,8-Tetrachlorodibenzo(p)dioxin (TCDD) has been known to induce inflammatory signaling in a number of cell types and tissues. We found that in U937 macrophages TCDD causes rapid activation of cytosolic phospholipase A2 (cPLA2) within 30 min as judged by the increase in the serine 505 phosphorylated form of cPLA2 protein and the increased cellular release of free arachidonic acid. This initial action of TCDD is accompanied with the up-regulation of an important inflammation marker, COX-2 mRNA expression within 1 h, and by 3 h, several other markers become up-regulated. These effects appear to be dependent on the initial increase in the intracellular concentration of Ca²⁺, and activation of cPLA2 and COX-2. A comparative study among three different human cell lines showed that activation of COX-2 within 1 h of action of TCDD is a common feature exhibited by all cell lines. On the other hand, the U937 macrophage line appears to be unique among them with respect to its ability to activate TNF-α and IL-8 mRNA expressions, and not requiring Src kinase in propagating the initial signaling of cPLA2. Based on the rapidity of activation of cPLA2 and COX-2, which occurs within 1 h of cell exposure to TCDD, when no change in mRNA expression of CYP1A1 has been observed, it is apparent that this unique action of TCDD is carried out through a distinct “nongenomic” pathway which, is clearly discernable from the classical, “genomic” action pathway of the AhR by not requiring the participation of ARNT.     

Comparison effect of feedstock to inoculum ratios on biogas yields of cafeteria,vegetable, fruit wastes with cattle manure using co-digestion process

Cafeteria, vegetable, fruit, and cattle manure are available year around at low cost and have the potential to complement each other for anaerobic digestion (AD). The objectives of this study were to determine the preferred mixing ratios and effects of feedstock to inoculum ratios for the optimal biogas production. The mesophilic digestion tests were performed with five mixing ratios of CW, VW, FW with CM and five feedstock to inoculum (F/I) ratios using batch anaerobic digesters. Co-digestion of CW, VW, FW with CM was carried out at F/I ratios of 1.0, 2.0, 3.0, 4.0, and 5.0. The results showed that the F/I ratio significantly affected the biogas production rate. Increasing the CW, VW, FW in the CM resulted in an increased methane yield by decreasing the F/I ratios in the reactors from 5.0 to 1.0. The highest biogas yields of 591.3, 432.9, and 450.6 L/kg VS_feed were obtained with CW/CM (50:50), VW/CM (25:75), and FW/CM (25:75) ratios, respectively. At five F/Is tested, after 45 days of AD, the total biogas yields were determined to be 629.74, 552.64, 501.87, 464.66, and 396.04 L and 496.93, 460.02, 420.5, 398.14, and 336.20 L, and 455.03, 382.81, 349.78, 340.95, and 298.53 L, respectively. However, the highest average CH₄ contents obtained at an F/I of 1.0 were 62.14%, 60.72%, and 61.08% that are 5.87%, 9.47%, and 10.17% higher than those obtained at F/I ratio of 5.0 for CW/CM (50:50), VW/CM (25:75), and FW/CM (25:75), respectively.     

Analysis method for PCBs in reclaimed oil using a fast-GC triple stage quadrupole mass spectrometer with the 13-component quantitation method

It is necessary for companies supplying reclaimed oil to analyze polychlorinated biphenyls (PCBs), because there is a possibility of the presence of contaminants due to trace-level PCBs in the reclaimed oil. However, common analysis methods of PCBs are time-consuming and complicated. Fast-GC triple stage quadrupole mass spectrometer with the 13-component quantitation method is an official method for analyzing PCBs in insulating oil in Japan. This method is extremely fast and simplified. The purpose of this study involves an investigation of the aforementioned fast and simple method for potential use in the analysis of reclaimed oil. Furthermore, it was attempted to combine the method with sample preparation involving only hexane dilution. The effect of sample dilutions corresponding to 100, 300, and 500 times was evaluated for reducing the matrix effect. The matrix effect was suppressed at a dilution ratio equal to or exceeding 300 times. Calibration curves of four points, namely 0.01, 0.05, 0.1, and 0.5 ng/mL, (ignored origin) by using an internal standard method were prepared for the 13 components. The square of regression coefficient (R²) values of all calibration curves exceeded 0.997. This method was adopted for the analysis of reclaimed oil containing 0.5 μg/mL PCBs, which corresponds to the judgment criteria, and accurate quantitation (accuracy value, 94.0–102%) and good repeatability (%RSD, 3.6%) were obtained. Furthermore, the required sensitivity was maintained even when 800 samples were analyzed without a cleaning ion source and an exchanging analysis column.     

The dynamics of mercury around an artisanal and small-scale gold mining area,Camarines Norte,Philippines

Environmental Science and Pollution Research - To elucidate the dynamics of mercury emitted and released by artisanal and small-scale gold mining (ASGM) activity and to estimate its impact on the...     

Changes in Chlorinated Organic Pollutants and Heavy Metal Content of Sediments during Pyrolysis (7 pp)

Background There has been an increasing concern about the treatment and disposal of contaminated sediment from dredged river, harbor or estuary due to the accumulated toxic organics such as dioxins and inorganics particularly heavy metals like Cr, Pb, Zn, Cu, Hg and Cd. However, considering the huge amount of materials and financial costs involved, any candidate technology must ultimately result to reusable residual by-products. This can only be made possible if the toxic pollutants are removed or stabilized in the raw sediment and then fed back into the materials cycle. Currently, we are developing a pyrolysis process for the commercial-scale cleanup of dioxins and heavy metal-contaminated river sediment to yield reusable char for various economical applications. In this connection, this paper describes our preliminary investigation into the extent of dioxins and heavy metal volatilization from actual contaminated sediment. The stabilization of certain metallic species particularly Cr ions was studied. Methods Laboratory scale pyrolysis experiments were conducted using a special horizontal lab-scale pyrolyzer. Sediment samples from Shanghai Suzhou Creek and Tagonoura Harbor were pyrolyzed in the reactor under nitrogen gas at 800°C and different retention times of 30, 60 and 90 min. A constant heating rate of 10°C min-1 was employed. The pyrolysis gas was first allowed to pass through a cold trap to condense the tar. Uncondensed gases were then channeled through a column containing an adsorbent (XAD-2 Resin) for dioxins. Heavy metal concentrations in the initial and final sediment residues were analyzed by ICP (Nippon Jarrel-Ash) following their acid and alkali (for Cr6+) digestion. Dioxins content of the pyrolysis char, tar, and exhaust gases in the dioxin adsorbent were also determined. For comparative purpose, thermal treatment under air flow was conducted. Results The data for the removal of heavy metals from Suzhou Creek sediment showed very significant reductions in Pb, Zn and Cr6+ content of the sediment at this condition. Percentage removals were 42.4%, 60.8% and 42.2%, respectively. The disappearance of Cr6+ was due to reduction reactions rather than volatilization since the total Cr content remained almost unchanged. Other heavy metals such as Cu, Fe and Ni showed very minimal reductions. Nonetheless, Toxicity Characteristics Leaching Procedure (TCLP) tests confirmed that these residual heavy metals were rather stable in the pyrolysis char. Reduction of toxic Cr6+ at 42.2% has also been achieved by pyrolysis (with N2) as opposed to the more than 580 % increase in Cr6+ observed during thermal oxidation (with air). Discussion Pyrolysis also remove toxic organics particularly dioxins from the sediment. For the total dioxins, removal percentage of 99.9999% was achieved even at the lowest retention time of 30 min. Almost all polychlorinated dibenzo-p-dioxine (PCDDs) and polychlorinated dibenzo-furans (PCDFs) were removed at any retention time. The TEQs detected from the solid residues were mainly contributed by dioxin-like PCBs, yet these were present in relatively trace quantities. At the shortest retention time of 30 min, only 0.000085 pg-TEQ g-1 of polychlorinated biphenyls (PCBs) was detected in the pyrolysis char. Furthermore, the residual PCBs have very low toxicity ratings and none of the highly toxic PCBs, which were initially present in the sediment such as 3,3',4,4',5-PeCB and 3,3',4,4'5,5'-HxCB, were detected in the char. Results further confirmed that most of the dioxins that were removed were transferred to the gas phase so that volatilization may be considered as the main mechanism for their removal. Conclusion Some heavy metals particularly Pb and Zn can be volatilized under N2 pyrolysis at 800oC. Pyrolysis also prevented the formation of more toxic Cr6+ ions and at the same time resulted to its reduction by around 42.2% contrast to the 580% increase during thermal oxidation. PCDDs and PCDFs have been removed and were not formed in the solid products over the retention time range of 30-90 min at 800°C. Dioxin-like PCBs mostly remained and a retention time of 30 min was found sufficient for its maximum removal. Recommendations and Perspective . With the above results, a temperature of 800oC at a retention time of 30 min is sufficient for the removal of total dioxins and some heavy metals by volatilization. It is however necessary to destroy the dioxins as well as recover heavy metals in the gas phase. Stability of remaining heavy metals in the char also needs to be confirmed by leaching tests. These are the major concerns, which we are currently evaluating to establish the feasibility of our proposed large scale pyrolysis system for sediment treatment.     

Micro fabrication on cylinder surface for control of wettability

A micro fabrication is presented to control wettability on cylinder surfaces. A machine tool is developed to form the micro-scale structure on the cylinder in incremental stamping. The stamping tool is manufactured with fabricating the micro-scale structure on the top of the tool in FIB sputtering. The micro incremental stamping is repeated with linear motion of the tool and rotation of the workpiece. The rotation is controlled by the friction drive on the machine table because of the stable stamping with reducing bending of the workpiece. The critical stamping depth, the minimum depth in which the structure is formed, is determined in the forming tests using the structured tool. Then, a stripe type structure is formed to control wettability on the cylinder surface. Anisotropic wettability appears on the structured surface.     

Biodegradable water-soluble polycarboxylic acid design: Biodegradability and builder performance in detergent formulation of partially dicarboxylated polyuronide containing sugar residues in the backbone

Partially dicarboxylated polyuronide having a variable amount of unreacted sugar blocks as an enzymatically cleavable segment was prepared by the controlled oxidation of pectic acid and alginic acid. It was found that partially dicarboxylated polyuronides containing uronide blocks showed better biodegradability than those having no uronide block in the polycarboxylate chain. The rate of biodegradation varies according to the degree of dicarboxylation. It was confirmed that dicarboxy polyuronides containing more than 70% unreacted uronide residues tended to biodegrade quickly. The biodegradability obtained by the BOD test and the enzymatic degradability are well correlated, suggesting that these polymers are first cleaved at the sugar blocks by carbohydrase with subsequent assimilation of the resultant oligomeric fractions. Detergency was dependent on the content of the carboxylate groups in the polymer. The polymers with high carboxylate contents showed better builder performance. The detergency of dicarboxy pectic acid was better than that of dicarboxy alginic acid when compared on the basis of an equal degree of dicarboxylation.     

Micro dimple milling on cylinder surfaces

The paper presents a micro dimple machining on a cylinder surface with a two-flutes ball end mill. When the cutter axis is inclined and the depth of cut is less than the tool radius, non-cutting time, during which neither of the two cutting edges contacts the workpiece, appears in a rotation of the cutter. The rotation of the workpiece and the feed of the tool are controlled so that the cutting areas do not overlap each other. In order to incline the tool with respect to the tangential direction on the cylinder surface, the tool is located at a position oriented at 45° from the top of the cylinder. An analytical model is presented to control the shapes of the dimples with the cutting parameters. The presented machining is verified in cutting tests with measuring the shape and the profile of the dimples. Pre-machining operations are conducted to have a high cylindricity of the workpiece in longitudinal turning and polishing. The cutter runout of the tool is also eliminated by adjusting the orientation and the position of the tool in the collet chuck with measuring the cutting force. The micro dimples are machined accurately as they are simulated.