Current state of yusho and prospects for therapeutic strategies

The mass food poisoning incident yusho occurred in Japan in 1968. It was caused by the ingestion of rice bran oil contaminated with polychlorinated biphenyls and various dioxins and dioxin-like compounds including polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDFs). Notably, PCDFs were found to contribute to approximately 65% of the total toxicity equivalent in the blood of yusho patients. Lipophilic dioxins are retained in the body for a longer period than previously estimated. Victims suffered from characteristic skin manifestations associated with non-specific systemic symptoms, neurological symptoms, and respiratory symptoms. The severe symptoms seen in the initial phase subsequently faded, but recently, improvements have scarcely been observed. The Yusho Group has been researching treatments for this condition. Several clinical trials with chelating agents or dietary fibers aimed at accelerating the excretion of compounds. While some treatments increased dioxin excretion, none provided satisfactory symptom relief. Concurrently, various phytochemicals and herbal extracts have been found to possess biological activities that suppress dioxin-induced toxicity via aryl hydrocarbon receptor or activate the antioxidant nuclear factor-erythroid 2-related factor-2 (NRF2) signal pathway, making them promising therapeutic candidates. Here, we summarize the current status of yusho and findings of clinical trials for yusho patients and discuss the treatment prospects.

     

Bioaccumulation surveillance in Milford Haven Waterway

Biomonitoring of contaminants (metals, organotins, polyaromatic hydrocarbons (PAHs), PCBs) was undertaken in Milford Haven Waterway (MHW) and a reference site in the Tywi Estuary (St Ishmael/Ferryside) during 2007–2008. Bioindicator species encompassed various uptake routes—Fucus vesiculosus (dissolved contaminants); Littorina littorea (grazer); Mytilus edulis and Cerastoderma edule (suspension feeders); and Hediste (=Nereis) diversicolor (sediments). Differences in feeding and habitat preference have subtle implications for bioaccumulation trends though, with few exceptions, contaminant burdens in MHW were higher than the Tywi reference site, reflecting inputs. Elevated metal concentrations were observed at some MHW sites, whilst As and Se (molluscs and seaweed) were consistently at the higher end of the UK range. However, for most metals, distributions in MH biota were not exceptional. Several metal-species combinations indicated increases in bioavailability upstream, which may reflect the influence of geogenic/land-based sources—perhaps enhanced by lower salinity. TBT levels in MH mussels were below OSPAR toxicity thresholds and in the Tywi were close to zero. Phenyltins were not accumulated appreciably in M. edulis, whereas some H. diversicolor populations appear subjected to localized (historical) sources. PAHs in H. diversicolor were distributed evenly across most of MHW, although acenaphthene, fluoranthene, pyrene, benzo(a)anthracene and chrysene were highest at one site near the mouth; naphthalenes in H. diversicolor were enriched in the mid-upper Haven (a pattern seen in M. edulis for most PAHs). Whilst PAH (and PCB) concentrations in MH mussels were mostly above reference and OSPAR backgrounds, they are unlikely to exceed ecotoxicological thresholds. Bivalve Condition indices (CI) were highest at the Tywi reference site and at the seaward end of MH, decreasing upstream—giving rise to several significant (negative) relationships between CI and body burdens. Despite the possible influence of salinity gradient as a complicating factor, multivariate analysis indicated that a combination of contaminants could influence the pattern in condition (and the biomarkers metallothionein and TOSC). Integrating bioaccumulation data with biological and biochemical endpoints is seen as a useful way to discriminate environmental quality of moderately contaminated areas such as MHW and to prioritise cause and effect investigations.     

Designing a purification process for chromium-, copper- and arsenic-contaminated wood

The disposal of chromated copper arsenate (CCA)-treated wood is becoming a serious problem in many countries due to increasing levels of contamination by the hazardous elements, chromium, copper and arsenic. The present experiment was conducted as a preliminary step toward one-step solvent extraction of CCA-treated wood. Because chromium, copper and arsenic have different chemical characteristics, it is best to consider them separately prior to designing a one-step extraction process. As a basis, various two-step extraction processes were first designed and tested experimentally to determine feasibility. Among these combinations, the treatment combining oxalic acid as the 1st step and a sodium oxalate solution under acidic conditions (pH 3.2) as the 2nd step was found to be an effective way of extracting CCA elements from treated wood. Extraction efficiency reached 100% for arsenic and chromium and 95.8% for copper after a 3-h sodium oxalate treatment, following a 1-h pre-extraction process with oxalic acid. On the other hand, the same combination under alkaline conditions (pH 11.2) during the 2nd step was ineffective for copper removal, indicating that pH plays an important role in complexation with sodium oxalate solution. The present results suggest that the extraction of CCA elements using a combination of oxalic acid and acidic sodium oxalate solution is a promising basis for application to a one-step extraction method.     

Population structure and life cycle of the mesopelagic ostracod Conchoecia pseudodiscophora in Toyama Bay,southern Japan Sea

The population structure and life cycle of the mesopelagic ostracod Conchoecia pseudodiscophora Rudjakov in Toyama Bay, southern Japan Sea, were investigated using a time-series of samples collected during 0 to 500 m vertical hausls with twin-type Norpac nets (0.35 and 0.10 mm mesh) over one full year (1 February 1990 to 30 January 1991). Additional samples were also collected with a single-type closing Norpac net (0.06 mm mesh) to examine the vertical distribution patterns of eggs and all instars of this species. The proportion of gravid females present indicated that reproduction of C. pseudodiscophora continues throughout the year, but peaks in April–July. Eggs and Instars I and II were distributed below 500 m, while the more advanced instars were most abundant in the 350 to 500 m stratum by both day and night. Based on the abundance peaks of each instar in the time-series samples, development times were estimated to be 2.5, 4, 3, 7 and 11 mo for Instars III, IV, V, VI, and VII, respectively. Thus, a total of 30 mo is required for newly spawned eggs to hatch and reach adulthood. Stomach-fullness indexes revealed no seasonality in the feeding activity of any instar stage, but that feeding activity was low in older instars, particularly in adult males. The present results are compared with those for a few other ostracod species, in an attempt to characterize the life cycle of C. pseudodiscophora inhabiting waters of subzero temperature in the mesopelagic zone of the Japan Sea.     

Mass spectrometric study of secondary organic aerosol formed from the photo-oxidation of aromatic hydrocarbons

From measurements by an Aerodyne Aerosol Mass Spectrometer (AMS), secondary organic aerosol (SOA) formed in laboratory chambers is believed to be less oxidized than well-oxidized ambient organic aerosol (OA). However, the mass spectrum of SOA formed from the photo-oxidation of aromatic hydrocarbons has not been sufficiently studied by using AMS though these reactions are potential sources of urban SOA. In this study, we studied SOA formed from the photo-oxidation of seven aromatic hydrocarbons by using Time-of-Flight AMS. Strong mass signals from SOA were found at m/z 43 (m43) and 44 (m44) in all the experiments. The m44 to total organic aerosol mass ratio (m44/OA) increased with irradiation time. For example, the m44/OA ratio increased from 10.6% to 13.3% during irradiation for 11 h in an experiment with toluene. The average m44/OA ratios were determined to be 5.8–17.1% for all the experiments. The m44/OA decreased and the m43/OA increased with increasing number of alkyl substituents of precursor aromatic hydrocarbons. This is because low-reactive ketones are preferentially produced rather than aldehydes with increasing number of alkyl substituents. The m44/OA ratios of the benzene and monoalkylbenzene oxidation were 12.2–17.1% and were close to those of well-oxidized ambient OA. These findings are consistent with the hypothesis that the photo-oxidation of aromatic hydrocarbons is a potential source of urban SOA. In addition to oxygenated organic compounds, organic nitrogen oxides were also shown to be present in SOA by high-resolution mass spectra.     

A novel extractant for removal of hazardous metals from preservative-treated wood waste

The purpose of this study was to develop a one-step metal extraction process that would effectively remove hazardous elements from wood powder or chips of western hemlock [Tsuga heterophylla (Raf.) Sarg.] treated with chromated copper arsenate (CCA) preservative. In addition, we tested this method for wood treated with other copper-based preservatives such as ammoniacal copper quaternary (ACQ) and copper, boron, and azole (CuAz). A bioxalate solution consisting of 0.125 M oxalic acid adjusted to pH 3.2 with sodium hydroxide was tested for its ability to extract chromium, copper, and arsenic from wood treated with CCA and copper from ACQ, CuAz, or a mixture of CCA-, ACQ-, and CuAz-treated wood in single step. The extraction proceeded efficiently with 6 h of treatment, and was insensitive to the differences in chemical characteristics, including solubility of individual elements. After 6 h of treatment, approximately 90% of chromium, copper, and arsenic were effectively removed from wood treated with CCA or a mixture of CCA, ACQ, and CuAz and 90% of copper from ACQ- and CuAz-treated wood. These results demonstrate that the solvent extraction technique using pH-adjusted bioxalate solution with sodium hydroxide is a promising method for pollution minimization by various types of wastes contaminated with heavy metals and arsenic.     

Characteristics of a bioxalate chelating extraction process for removal of chromium,copper and arsenic from treated wood

The disposal of wood waste treated with chromated copper arsenate (CCA) is a problem in many countries. We have proposed a novel chelating extraction technique for CCA-treated wood using bioxalate, a solution of oxalic acid containing sufficient sodium hydroxide to adjust the pH to 3.2, which is an effective way to obtain an extraction efficiency of 90% for chromium, copper, and arsenic. The purpose of the present study was to investigate the characteristics of bioxalate extraction of CCA-treated wood. Extractions of CCA-treated western hemlock chips with solutions of bioxalate, oxalic acid, and sodium hydroxide were carried out. The use of bioxalate was confirmed as the most effective extraction technique for chromium, copper and arsenic, with an efficiency of 90%. Extraction with simple oxalic acid was ineffective for copper (less than 40% extraction efficiency), but effective for chromium and arsenic, with 90% efficiency. Sodium hydroxide showed a similar tendency, being ineffective for chromium and copper (less than 20% extraction efficiency), but relatively effective for arsenic (around 70–80% efficiency). We also discovered an interesting phenomenon whereby the addition of sodium hydroxide to a simple oxalic acid solution during the oxalic acid extraction progress resulted in dramatically increased extraction efficiency for copper, chromium and arsenic, up to 90%. Although oxalic acid was ineffective for copper extraction, the addition of sodium hydroxide during the oxalic acid extraction process rendered it effective.     

Influence of a collapsed coastal landfill on metal levels in sediments and biota--a portent for the future?

In May 2008 a coastal landslide deposited landfill debris onto the shore near Lyme Regis, UK. Six months later, intertidal sediments and biota from the area were sampled to determine whether the landslip had affected distribution and bioavailability of metals in the area and if there were any biological effects. Highest sediment concentrations for the majority of metals occurred near the landslip zone and in several cases exceeded Threshold Effects or Probable Effects Levels (As, Cu, Hg, Ni, Pb, Zn). The 1 M HCl-extractable fraction of Cd, Pb and Zn in sediments also increased near the landslip. Metal bioaccumulation by intertidal biota showed variability between different species and metals, but there were several instances of increased accumulation near the landslip through increased availability from seawater, sediment and dietary sources. In most cases, metal concentrations in molluscs exceeded Oslo and Paris Commission (OSPAR) background concentrations (BCs) together with background assessment concentrations (BACs) at some sites. Kidney tissues in winkles (Littorina littorea) were measured for evidence of oxidative stress using the Total Oxyradical Scavenging Capacity (TOSC) assay. Responses to peroxynitrite, peroxyl and hydroxyl radicals suggested raised levels of TOSC in animals from the sites close to or east of the landfill waste. There have been very few studies of direct impact of landfills on the marine environment and this study could serve as a practical model for similar events driven by sea level rise.     

Fungal biodegradation of CCA-treated wood and removal of its metal components

In the present study, 5 isolates of brown-rot fungi were used for fungal bioprocessing (FB) of chromated copper arsenate (CCA)-treated wood wastes: Antrodia vaillantii SEL8501, Fomitopsis palustris TYP0507 and TYP6137, and Crustoderma sp. KUC8065 and KUC8611. The isolates showed notable capacity for the degradation of treated wood and removal of CCA components via the American Wood Protection Association soil block test. Among them, Crustoderma sp. KUC8611 effectively decayed the treated wood, causing a mass loss of up to 60%. F. palustris caused extensive leaching of CrO₃ of up to 79% and As₂O₅ of up to 87%, but only moderate leaching of CuO of up to 50%. This high capacity for removal of CrO₃ and As₂O₅ showed a strong logarithmic relationship with the amount of oxalic acid produced in the decayed wood. The majority of metals removed from treated wood during the decay process were deposited in the soil and feeder strip. Further investigation will be required to establish the capability of selected fungi for FB of full-sized lumber treated with CCA.