Probability Density Functional Method of Enzyme Effect on Denatured Protein Soil.

Protein soils must be removed for both appearance and hygienic reasons. They are denatured by heat treatment or bleaching and cleaned using enzymes. Among the various types of protein soils, blood soils are the most noticeable and known to be denatured by heat and bleaching by oxidation. We verified herein that the detergency of heat and oxidatively denatured hemoglobin is greatly improved by the enzyme immersing treatment in the detergency with SDS and can be analyzed using the probability density functional method. The probability density functional method evaluates the cleaning power by assuming that the adhesion and cleaning force of soils are not uniquely determined, but instead have a distribution in intensity, with a usefulness that had recently been demonstrated. This analytical method showed that the cleaning power of the enzyme immersing treatment improved when the soil adhesive force was decreased due to denatured protein degradation, even though the cleaning power of the SDS remained unchanged, and the values were consistent with those in the cleaning test. In conclusion, the probability density functional method can be used to analyze enzymatic degradation of denatured protein soils and the resulting changes in their detergency.

Improving the Removability of Mud Stains by Combining a Homopolymer and a Chelating Agent.

To improve the detergency of mud stains without triphosphate, we developed a new composition that enhances the detergency of mud stains more efficiently. To develop the composition, a new correction method based on the probability density functional method was used to compare the results of approximately 100 cleaning tests conducted on different days using various active ingredients. As a result of various evaluations, it was found that the combination of a homopolymer with a molecular weight of approximately 2000 and a chelating agent can effectively improve the detergency of particle stains. By combining washing experiments with different polymer concentrations, water hardness, turbidity, and reduced viscosity, we were able to estimate the expansion of the polymer and the washing mechanism using a combination of low-molecular-weight polymers and chelating agents.

Effects of adsorbent carriers in modified ready biodegradability tests of quaternary ammonium salts.

Standard ready biodegradability tests are conducted at unrealistically high test concentration and therefore cannot properly evaluate toxic substances to microorganisms. The present study evaluated the effects of four adsorbent carriers in modified ready biodegradability tests of four quaternary ammonium salts (QASs) demonstrating microbial toxicity according to the Organization for Economic Co-operation and Development Test Guideline 301F and cautions for using carriers were found. In the tests with silica gel, the concentration of all QASs in the test solutions decreased due to adsorption. The percentages of biodegradation of octadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, and benzyldimethyloctadecylammonium chloride, which have a linear alkyl chain, were 89.9%, 80.6%, and 70.1% on day 28, respectively; benzethonium chloride, with a branched alkyl chain, did not undergo biodegradation. In the tests with activated carbon, although the concentrations of QASs greatly decreased, no QASs underwent biodegradation. In the tests with sea sand or quartz sand, QASs were not adsorbed on the carriers and were not biodegraded. Using an adsorbent carrier for toxic substances will increase biodegradation, but it has no effect on highly persistent substances with specific chemical structures, e.g., branched carbons, which is very important because ready biodegradability is not overestimated. Carriers having moderate adsorbability should be selected.

Identification of a mutagenic chlorination by-product produced from (E)-1, 3-dichloropropene (a component of nematocide DD) by using high resolution LC/MS and multivariate analysis.

The estimated domestic usage of DD (a typical nematocide) has been the greatest among all the agricultural chemicals in Japan. DD is involved in a document which is used to establish tap water quality standard in Japan. The document indicates that DD is potentially detectable in raw water for tap waters. DD in raw water will be treated with chlorine at waterworks, which raises concerns about formation of mutagenic chlorination by-products through the treatment. The objective of this work was to identify a mutagenic chlorination by-product by using high resolution mass spectrometers and multivariate analyses. Mutagenicity of the chlorination by-product was evaluated with the Ames Salmonella mutagenicity assay. (E)-1,3-Dichloropropene (DCP) was used as a model compound of DD. The mutagenicity of chlorine treated model aqueous solutions of DD increased with increasing chlorine dosages up to 3.00 mol-Cl2/mol-DCP. From the chlorine treated aqueous solutions of DD, 1,3-dichloroacetone (DCA) was identified as a major mutagen by a cochromatography with an authentic standard, precursor ion analyses and first-generation product ion analyses with the high resolution mass spectrometers. The mutagenicity of DCA against TA100 strain without microsomal activation was 160,000 net revertant colony/µmol (the toxicity equivalent factor was 0.14). Based on the mutagenicity of the chlorine treated DCP sample, the specific mutagenicity of DCA, and the DCA concentration in the sample, the mutagenic contribution of DCA to the chlorine treated DCP sample was calculated. High contribution (98%) clearly shows that DCA is a major mutagen in the chlorine treated DCP sample. Because the exploration of DCA was performed by using the unrealistic high concentration samples of DCP and chlorine, formation of DCA in the practical concentration samples (0-200 µg-DCP/L, 0.10 or 1.27 mg-Cl2/L) was examined. It was proven that DCA formation reaction takes place in the practical concentrations of DCA and chlorine.

Removals of pesticides and pesticide transformation products during drinking water treatment processes and their impact on mutagen formation potential after chlorination.

Removal efficiencies of 28 pesticide transformation products (TPs) and 15 parent pesticides during steps in drinking water treatment (coagulation-sedimentation, activated carbon adsorption, and ozonation) were estimated via laboratory-scale batch experiments, and the mechanisms underlying the removal at each step were elucidated via regression analyses. The removal via powdered activated carbon (PAC) treatment was correlated positively with the log Kow at pH 7. The adjusted coefficient of determination (r2) increased when the energy level of the highest occupied molecular orbital (HOMO) was added as an explanatory variable, the suggestion being that adsorption onto PAC particles was largely governed by hydrophobic interactions. The residual error could be partly explained by π-π electron donor-acceptor interactions between the graphene surface of the PAC particles and the adsorbates. The removal via ozonation correlated positively with the energy level of the HOMO, probably because compounds with relatively high energy level HOMOs could more easily transfer an electron to the lowest unoccupied molecular orbital of ozone. Overall, the TPs tended to be more difficult to remove via PAC adsorption and ozonation than their parent pesticides. However, the TPs that were difficult to remove via PAC adsorption did not induce strong mutagenicity after chlorination, and the TPs that were associated with strong mutagenicity after chlorination could be removed via PAC adsorption. Therefore, PAC adsorption is hypothesized to be an effective method of treating drinking water to reduce the possibility of post-chlorination mutagenicity associated with both TPs and their parent pesticides.

Identification of mutagenic transformation products generated during oxidation of 3-methyl-4-nitrophenol solutions by orbitrap tandem mass spectrometry and quantitative structure-activity relationship analyses.

We used Ames assays to investigate the effects of ozonation (designated O3), ozonation followed by chlorination (O3/Cl), an advanced oxidation process (AOP, UV/H2O2), and AOP followed by chlorination (AOP/Cl) on the mutagenicity of solutions of 3-methyl-4-nitrophenol (3M4NP), a major environmental degradation product of the organophosphorus insecticide fenitrothion. Whereas O3 did not induce mutagenicity, O3/Cl, AOP, and AOP/Cl converted 3M4NP into mutagenic transformation products (TPs). Using liquid chromatography-mass spectrometry, we detected a total of 138 peaks in the solutions subjected to O3/Cl, AOP, and AOP/Cl. To elucidate the TPs responsible for the observed mutagenicity, we performed simple regression analyses of the relationship between the area of each peak and the observed mutagenicity of samples withdrawn periodically during each oxidation process. The area of each of 10 peaks was found to be positively correlated (r2 ≥ 0.8) with the observed mutagenicity, suggesting that the TPs corresponding to these peaks contributed to the mutagenicity. After taking into account the consistency of mutagenicity induction by the oxidation processes and analyzing the peaks by tandem mass spectrometry, we identified 3 TPs, corresponding to 6 peaks, as candidate mutagens. These TPs were assessed by means of 4 quantitative structure-activity relationship (QSAR) models, and all 3 were predicted to be mutagenic by at least one model. This result was consistent with our assumption that these TPs were mutagens. Ames assays of an authentic sample of one of the 3 TPs revealed that it did not contribute to the mutagenicity. This left 3-methoxy-4-nitrophenol and 2-[(E)-[(2,5-dihydroxyphenyl) methylidene]amino]-5-dihydroxybenzaldehyde on the list of mutagens suspected of contributing to the mutagenicity induced by AOP. No TPs were identified as candidate mutagens responsible for the mutagenicity induced by O3/Cl and AOP/Cl.

Effect of test concentration in the ready biodegradability test for chemical substances: Improvement of OECD test guideline 301C.

In Japan, understanding the environmental persistence of chemicals is very important for risk assessment, and ready biodegradability tests are mainly conducted according to the Organisation for Economic Co-operation and Development test guideline 301C. However, the highest test concentration specified in test guideline 301C, 100 mg/L, may cause microbial toxicity and incomplete biodegradation. The authors performed test guideline 301C tests at test concentrations of 30 mg/L for 13 substances that were readily biodegradable in ready biodegradability tests but not in test guideline 301C tests. Of the 5 substances with potential to cause microbial toxicity at 100 mg/L, the percentage of biodegradation of sodium dimethyldithiocarbamate, 4-chloro-3-cresol (CC), thymol (THY), and p-tert-butyl-α-methylbenzenepropionaldehyde measured by biochemical oxygen demand (BOD) increased in the test guideline 301C test at 30 mg/L, suggesting a reduction in toxicity effects. Furthermore, CC and THY met the criteria for ready biodegradability, which are more than 60% of biodegradation by BOD and a 10-d window. Of the 8 substances with a low potential for causing microbial toxicity at 100 mg/L, the percentage of biodegradation of only 2-(diethylamino)ethanol increased in the test guideline 301C test at 30 mg/L. Employing a lower test concentration in the standard test guideline 301C test will contribute to improvement of consistency between results of a test guideline 301C test and other ready biodegradability tests.

Comparison study on observed and estimated concentrations of perfluorooctane sulfonate using a fate model in Tokyo Bay of Japan.

Perfluorooctane sulfonate (PFOS) was quantified in seawater and sediment samples collected from Tokyo Bay, Japan, ranging from 2.0 to 7.3 ng/L for surface seawater, 2.2 to 5.7 ng/L for intermediate seawater, 1.5 to 5.7 ng/L for bottom seawater, and 0.3 to 0.9 ng/g dry wt. for sediment. In addition, a 3-D chemical fate prediction model (National Institute of Advanced Industrial Science and Technology - Risk Assessment Model: AIST-RAM) has been applied to determine the accuracy of estimating PFOS in Tokyo Bay. A decreasing trend of PFOS from the northwestern part (i.e., the closed-off section of Tokyo Bay) to the mouth of the bay was observed, and the trend obtained from the actual surveys in this study was accurately represented by simulation with appropriate input parameters for AIST-RAM. From the comparison of observed concentrations with estimated concentrations, AIST-RAM showed a high degree of accuracy in estimating the concentrations of PFOS in seawater, whereas the estimations of PFOS concentrations in sediment had a relatively larger margin of error than those in seawater. However, our results indicate that AIST-RAM allows estimation of PFOS concentrations in seawater and sediment in Tokyo Bay with satisfactory accuracy.

A simple simulation of adsorption equilibrium of Pb(II) on Andosols in the presence of dissolved humic substances for monitoring soil contamination.

The adsorption equilibrium of Pb(II) on Andosols was investigated and described quantitatively in order to develop a simple method for the rapid monitoring of heavy metals in soils. The effect of solution pH on adsorption isotherms was investigated experimentally and in simulations. At pH 7, the considerable desorption of Pb(II) due to the extensive dissolution of humic substances (HS) from soils into aqueous phases is known to be an obstacle to carrying out simulations. In batch experiments, the total organic carbon (TOC) of the aqueous phases was shown to be enhanced by the addition of pre-extracted HS to soil suspensions. By combining the ion-exchange and Freundlich models, the adsorption equilibriums of free Pb(2+) ions and Pb(2+)-HS were simulated and were shown to be in good agreement with the experimental results. By estimating the concentrations and adsorption amounts of Pb(2+) and Pb(2+)-HS from measured CPb and TOC, it is possible to accurately simulate the soil contamination status even in in the presence of dissolved HS in the water in the solid-liquid extraction samples.

Ecological risk of estrogenic endocrine disrupting chemicals in sewage plant effluent and reclaimed water.

The long-term ecological risk of micropollutants, especially endocrine disrupting chemicals (EDCs) has threatened reclaimed water quality. In this study, estrogenic activity and ecological risk of eight typical estrogenic EDCs in effluents from sewage plants were evaluated. The estrogenic activity analysis showed that steroidal estrogens had the highest estrogenic activity (ranged from 10(-1) to 10(3) ng-E2/L), phenolic compounds showed weaker estrogenic activity (mainly ranged from 10(-3) to 10 ng-E2/L), and phthalate esters were negligible. The ecological risk of the estrogenic EDCs which was characterized by risk quotient ranged from 10(-4) to 10(3), with an order in descending: steroids estrogens, phenolic compounds and phthalate esters. The eight estrogenic EDCs were scored and sorted based on the comparison of the estrogenic activity and the ecological risk, suggesting that 17α-ethynylestradiol (EE2), estrone (E1) and estradiol (E2) should be the priority EDCs to control in municipal sewage plants.

A preliminary categorization of end-of-life electrical and electronic equipment as secondary metal resources.

End-of-life electrical and electronic equipment (EEE) has recently received attention as a secondary source of metals. This study examined characteristics of end-of-life EEE as secondary metal resources to consider efficient collection and metal recovery systems according to the specific metals and types of EEE. We constructed an analogy between natural resource development and metal recovery from end-of-life EEE and found that metal content and total annual amount of metal contained in each type of end-of-life EEE should be considered in secondary resource development, as well as the collectability of the end-of-life products. We then categorized 21 EEE types into five groups and discussed their potential as secondary metal resources. Refrigerators, washing machines, air conditioners, and CRT TVs were evaluated as the most important sources of common metals, and personal computers, mobile phones, and video games were evaluated as the most important sources of precious metals. Several types of small digital equipment were also identified as important sources of precious metals; however, mid-size information and communication technology (ICT) equipment (e.g., printers and fax machines) and audio/video equipment were shown to be more important as a source of a variety of less common metals. The physical collectability of each type of EEE was roughly characterized by unit size and number of end-of-life products generated annually. Current collection systems in Japan were examined and potentially appropriate collection methods were suggested for equipment types that currently have no specific collection systems in Japan, particularly for video games, notebook computers, and mid-size ICT and audio/video equipment.

Comparison of observed and estimated concentrations of volatile organic compounds using a Gaussian dispersion model in the vicinity of factories: an estimation approach to determine annual average concentrations and human health risks.

The concentrations of toluene and dichloromethane in the vicinity of factories that emitted a large amount of toluene or dichloromethane into the atmosphere were determined for the comparison of observed and estimated concentrations using a Gaussian dispersion model (METI-LIS model). Greater concentrations of toluene and dichloromethane than the guideline value described in the Air Quality Guidelines for Europe, second edition, were measured in the vicinity of factories (270 and 470 micro g/m(3) for toluene and 510 and 660 micro g/m(3) for dichloromethane). Toluene and dichloromethane may have some adverse health effects on the local population in the vicinity of the emission source. Although the estimated concentrations in the vicinity of the emission source by the METI-LIS model involved a large margin of error, the proposed correction approach with only one weekly measurement reduced the estimation error of annual average concentrations. The proposed method could be useful for the management of ambient environment of emission source, due to no difficulty in modifying the input parameters of METI-LIS that required highly specialized knowledge.

Application of biological safety index in two Japanese watersheds using a bioassay battery.

In order to integratedly evaluate the biological safety as a water quality index, an assessment method based on three toxicity tests (algae growth inhibition, daphnia immobilization and larval fish toxicity) was developed. In this study, the developed method was used to screen, evaluate and rank the biological safety of small rivers near agricultural, industrial and residential areas. Twenty-seven representative water samples were collected from the Kaname River watershed and the Hinata River watershed in Kanagawa Prefecture, Japan. The results indicated that (1) the biological safety of water from the Hinata River ranked much higher than those from the Suzu River and the Shibuta River due to less human activities, (2) the biological safety from outlets of paddy fields ranked much worse than those from point source discharges of toxic pollutants, (3) the use of pesticides significantly affected the water quality of nearby small rivers and ditches during the pesticide application season, (4) the effects of different kinds of pesticides could successfully be classified using one toxicity test component of the bioassay battery, and (5) there was no significant quantitative relationship between the toxicity and dissolved organic carbon (DOC) for the studied water samples. The toxicities of water samples in this study were in agreement with the concentrations of pesticides determined with chemical methods by other researchers, which demonstrated that the developed assessment method was reliable to screen site contaminated with organic chemicals for priority management.

Analysis of the toxicity-weighted release amount ranking of PRTR chemicals in Japan.

In this study, toxicity data were first collected for 184 chemicals from reliable information sources. After a validity check and analysis of these data, reference concentrations (RfC) were determined. The toxicity-weighted release amount (TWR) was then calculated for each chemical by dividing the release amounts by the RfC. Three types of TWR were derived, namely TWR(atm) for human health protection in the atmosphere, TWR(wat) for human health protection in water, and TWR(aq) for aquatic life protection. Thus, TWR could be proposed as a new index for environmental risk management considering both toxicity and release amount. Based on the TWR values, chemicals were ranked according to their potential risk upon release. The ranking results revealed that acrolein, formaldehyde, 1,3-butadiene, and arsenic are among the substances with the greatest risk to human health protection in the atmosphere; acrylonitrile, hydrazine, and pyridine are among those detrimental to human health protection in water; and polyoxyethylene alkyl ether (POAE), n-alkylbenzene sulfonic acid (LAS), and N,N-dimethyldodecylamine N-oxide are those identified as posing a risk to aquatic life protection. Moreover, for higher TWR chemicals, the contribution of each release source has been analyzed and discussed. For example, POAE and LAS are released mainly from households, and therefore efforts to reduce their concentration in the environment should focus on the sewage system. Formaldehyde and 1,3-butadiene are mainly emitted from mobile sources and, therefore, traffic should be evaluated as an important release source of toxic chemicals besides many stationary sources. Acrylonitrile and arsenic are released mainly by a few specific industries, placing the emphasis on the need for responsible care by the individual companies involved.

Environmental management of pesticidal POPs in China: past, present and future.

China, the largest developing country in the world, has been undergoing rapid economic growth in the past two decades. Synchronously, large quantities of persistent organic chlorinated pesticides have been used in agriculture and non-agriculture areas. Accompanying with incomplete management framework, the improper use and disposal of pesticides have caused serious pollution problems. In this study, we discussed: (1) ten persistent organochlorine pesticides in terms of historical production, consumption and number of manufacturers, import and export; (2) the current management framework of pesticidal persistent organic pollutants (POPs) with respect to legal system and government administrative system; (3) the existing problems in the management of pesticidal POPs; and proposed recommendations for countermeasures. Based on the available information, it can be concluded that records on the historical production and consumption quantities of pesticidal POPs are incomplete which makes a difficulty in the management. Although China has come a long way in developing a modern legal system, the current system is still considered weak and inefficient; and many challenges are ahead. The government administrative system has also been reformed and improved, but over-lapping jurisdictions still exist and are ineffective in managing pesticidal POPs program. To address these existing problems in pesticidal POPs management, it was suggested that more investigations should be conducted to collect information on pollution sources of pesticidal POPs, to evaluate their environmental risks, to identify new alternative chemicals and to complete management framework of pesticidal POPs in China. Furthermore, the public should be encouraged to participate in managing hazardous pesticidal POPs in China, and international cooperation and communication should be established and strengthened imperatively as well.

Evaluating the fish safety level of river water and wastewater with a larval medaka assay.

A larval medaka (Oryzias latipes) assay was proposed to evaluate the fish safety level of river waters and wastewaters. Organic toxicants were 10-100 times concentrated with adsorption cartridges from 4 l of river water or 1-10 times concentrated from 400 ml of wastewater. Toxicity of these concentrated solutions was determined by exposing 48-72 h post-hatch age larvae for 48 h. The method effectively revealed a variation of the median lethal concentration ratio (LCR50) from 13 to >100 in 125 river water samples, and from <1 to >10 in five typical wastewater samples. Ayase River, which takes water mostly from agricultural or household discharge, showed significantly (P<0.001) lower LCR50 than Sagami River that takes natural water as the source. Safety Levels in both Sagami River and Ayase River were influenced by the irrigation activity, LCR50 at some sites showing a seasonal-specific decrease in winter. Pollution from pulp and paper industries contributed to the low LCR50 in several tributaries of Ayase River. Required little manpower in sampling, pretreatment and testing, the proposed larval medaka assay was proved as an efficient tool for screening those high risk sites for priority management.

Application of a larval medaka assay to evaluate the fish safety level in Sagami River, Japan.

Despite of the increasing concern on aquatic life preservation from water pollution, few methods are available to evaluate the fish safety level of river water. In this study, a principal urban river of Japan, Sagami River, was investigated the geographical and seasonal changes in the fish safety level using an efficient larval medaka (Oryzias latipes) assay. Then combined with topography and land-use character of the catchment, the influence of human activity was discussed. The results revealed the highest fish safety levels and the lowest dissolved organic carbon (DOC) concentrations in the preserved region of the upstream. In the lower mainstream and the west tributaries, catchments of which were developed regions with high sewerage diffusion rates, the fish safety levels slightly decreased although the DOC concentrations were low. By comparison, the east tributaries, which were allocated in highly developed regions without sufficient sewerage service, showed not only high DOC concentrations but also greatly decreased fish safety levels. Two small east tributaries showed three to four times increase in the toxicity in winter, as influenced by the irrigation activity on the bank. The safety level did not closely depend on the common water quality indicator of DOC, although extremely high DOC concentrations tended to relate to low safety levels. The data is useful for better management of the river studied, and the approaches used in this paper will give a hint to the management of other rivers.

A new method for evaluating biological safety of environmental water with algae, daphnia and fish toxicity ranks.

In this study, an innovative approach to evaluate biological safety of environmental water with toxicity ranks was proposed. Widely used species, algae (Selenustrum capricornutum), daphnia (Daphnia magna) and fish (Oryzias latipes larvae) belonging to three trophic levels in aquatic ecosystem, were selected and combined as a test set to measure the bio-toxicity of water sample. Maximum exposure concentrations for algae, daphnia and fish test were respectively designed as 10-, 50- and 50-fold of river water based on a simplification of conventional toxicity extrapolation method EU Directive EEC/93/67. A novel assessment index "safety score" of 1, 2, 3 and 4 with 1 being the safest was established for normalizing the toxicity effects. Safety score was determined according to the highest exposure concentration where adverse ecotoxicological effects could not be observed, and a triangle figure was designed to visually describe the safety scores of three toxicity tests. Finally, in order to conveniently evaluate the biological safety of environmental water, an integrated assessment index "bio-safety rank" (BSR) was established and determined according to the safety scores of the three tests, and with the index BSR, water sample could be ranked as A, B, C or D with A being the safest. It was shown that the proposed new method was effective for screening and evaluating the biological safety of river water in case studies.