Levels and distributions of hexachlorobutadiene and three chlorobenzenes in biosolids from wastewater treatment plants and in soils within and surrounding a chemical plant in China.

Although hexachlorobutadiene (HCBD) was recently proposed as a candidate persistent organic pollutant (POP) under the Stockholm Convention, information about its environmental levels and distributions is still very limited. In this work, HCBD was determined in the sewage sludge from 37 wastewater treatment plants (WWTPs) in 23 cities and 17 soils near a chemical plant in China. Three chlorobenzenes (CBs) (1,2,4-trichlorobenzene, 1,2,4,5-tetrachlorobenzene, and hexachlorobenzene) were simultaneously studied to help better understand the environmental behavior of HCBD. Concentrations of HCBD in sludge samples ranged from <0.03 to 74.3 ng/g dry weight (dw) with a median value of 0.30 ng/g dw, which was lower than those of the three CBs. Levels of HCBD were not correlated with capacity of the WWTPs and total organic carbon. For soils, high level of HCBD was found in the sample within the plant, with a rapid decreasing concentration trend with the increase of distance from the plant. It was suspected that releasing as a byproduct during manufacturing of chlorinated chemicals was the primary source of HCBD in the studied location. Further risk assessment indicated that the environmental risk of HCBD to soil organisms and the health risk to employees were very low through soil exposure within the plant.

Systematic study of the contamination of wastewater treatment plant effluents by organic priority compounds in Almeria province (SE Spain).

The occurrence of priority organic pollutants in wastewater (WW) effluents was evaluated in a semi-arid area, characterized by a high agricultural and tourism activity, as Almeria province (Southeastern Spain). Twelve wastewater treatment plants (WWTPs) were sampled in three campaigns during 2011, obtaining a total of 33 WW samples, monitoring 226 compounds, including pesticides, polycyclic aromatic hydrocarbons (PAHs), phenolic compounds and volatile organic compounds (VOCs). Certain banned organochlorine pesticides such as aldrin, pentachlorobenzene, o,p'-DDD and endosulfan lactone were found, and the most frequently detected pesticides were herbicides (diuron, triazines). PAHs and VOCs were also detected, noting that some of these pollutants were ubiquitous. Regarding phenolic compounds, 4-tertoctylphenol was found in all the WW samples at high concentration levels (up to 89.7 µg/L). Furthermore, it was observed that WW effluent samples were less contaminated in the second and third sampling periods, which corresponded to dry season. This evaluation revealed that despite the WW was treated in the WWTP, organic contaminants are still being detected in WW effluents and therefore they are released into the environment. Finally the risk of environmental threat due to the presence of some compounds in WWTP effluents, especially concerning 4-tertoctylphenol must be indicated.

Coordination polymer adsorbent for matrix solid-phase dispersion extraction of pesticides during analysis of dehydrated Hyptis pectinata medicinal plant by GC/MS.

The coordination polymer [Zn(BDC)(H(2)O)(2)](n) was tested for extraction of pyrimethanil, ametryn, dichlofluanid, tetraconazole, flumetralin, kresoxim-methyl and tebuconazole from the medicinal plant Hyptis pectinata, with analysis using gas chromatography-mass spectrometry in selected ion monitoring mode (GC/MS, SIM). Experiments carried out at different fortification levels (0.1, 0.5 and 1.0 µg g(-1)) resulted in recoveries in the range 73-97%, and RSD values were between 5 and 12% for the [Zn(BDC)(H(2)O)(2)](n) sorbent. Detection and quantification limits ranged from 0.02 to 0.07 µg g(-1) and from 0.05 to 0.1 µg g(-1), respectively, for the different pesticides studied. The method developed was linear over the range tested (0.04-14.0 µg g(-1)), with correlation coefficients ranging from 0.9987 to 0.9998. Comparison between [Zn(BDC)(H(2)O)(2)](n) and the commercial phase C(18)-bonded silica showed good performance of the [Zn(BDC)(H(2)O)(2)](n) polymeric sorbent for the pesticides tested.

Determination of clofentezine in medical herb extracts by chromatographic methods combined with diode array scanning densitometry.

The aim of this study is to report a new procedure for extraction, cleanup and determination of clofentezine in herb extracts by ultrasound-assisted solvent extraction, SPE and multidimensional planar chromatography with diode array detector (MDPC-DAD) and/or HPLC-DAD. The application of various extraction solvents in SPE experiments conducted on octadecyl silane coupled with styrene-divinylbenzene cartridges for fractionation and purification samples has been described. Normal-phase systems were used in MDPC experiments on silica layer. The procedure described for the determination of compounds is inexpensive and can be applied to the routine analysis of analytes in plant extracts, after preliminary cleanup and concentration, e.g. by SPE. Application of MDPC-DAD and HPLC-DAD is especially useful for correct identification of components of difficult, complicated mixtures, e.g. analytes in medical herbs.

Leaf-air transfer of organochlorine pesticides from three selected vegetables.

The leaf-air transfer of organochlorine pesticides (OCPs) in three kinds of vegetables, namely lettuce, romaine and garlic leaves was investigated. It was found that although the uptake of OCPs by the three selected vegetables was similar under controlled conditions, the depuration varied significantly among chemicals and plant species in terms of elimination rate, final residue of each OCPs, as well as the effect of temperature on the residue of OCPs in the vegetables. The results indicated that neither QCB nor HCB could be trapped tightly by any of the three selected vegetables, in contrast, p,p'-DDT could be retained effectively by all of them; the retainment of alpha-HCH, gamma-HCH, p,p'-DDE, was dependent on the vegetable species, of which the garlic leaf had the biggest ability to trap them. Our work provided insight into the behavior of OCPs in the agroecosystem.

Levels of metals, PCBs, PCNs and PAHs in soils of a highly industrialized chemical/petrochemical area: temporal trend.

In 2005, the concentrations of various metals and organic pollutants were analyzed in soils collected in different areas of Tarragona (Catalonia, Spain), where an important chemical/petrochemical complex is located. The levels of seven elements (As, Cd, Cr, Hg, Mn, Pb and V), as well as those of polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs) and polycyclic aromatic hydrocarbons (PAHs) were determined in soils, and compared with those obtained in a background study carried out in 2002. Only Cd and Pb showed significant higher concentrations in the petrochemical zone, while no significant differences were found for the remaining elements. In turn, vanadium was the only element showing a significant increase in the concentration between 2002 and 2005. With regard to the organic pollutants, no significant differences were found according to the area of sampling. However, an increase in naphthalene levels was observed during the period 2002-2005 in soils of the chemical and petrochemical areas. According to the present results, it is suggested that the levels of vanadium must be periodically monitored to assure that the important industrialization of Tarragona does not mean health risks for the population living near the complex.

The estimation of NMVOC emissions from an urban-scale wastewater treatment plant.

The emissions of 19 different non-methane volatile organic compounds (NMVOCs) from the sewage treatment plant of the province of Eskisehir in Turkey were estimated. The estimations were based on the modified surface-renewal model suggested by EPA. The estimated total annual amounts of the pollutants emitted (from the plant's primary and secondary clarifier units and their weirs, as well as the aerated biological treatment unit) varied between a range of 0.00024 t (1,3-dichlorobenzene) and 0.1646 t (tetrachloroethylene). The corresponding flux data ranged from 9.98 x 10(-10)g cm(-2) h(-1) (1,3-dichlorobenzene) to 8450 x 10(-10)g cm(-2) h(-1) (tetrachloroethylene). Resulting total hourly NMVOC emission rate (0.041 kg h(-1)) was found not to exceed the current national standards. This work may be considered as a regional background for a possible contribution to the national and international emission inventory study on NMVOCs.

[Method-performance studies of notified analytical method for clofentezine].

Method-performance studies were conducted for the notified revised analytical method of clofentezine. Clofentezine spiked in azuki beans, apple, orange, banana, grape, tea powder and tea extract at the level of 0.2 microgram/g (2 micrograms/g for tea) was analyzed in replicate in 6 laboratories. Mean values of recovery from 7 crops ranged from 78.4 to 85.2%. Repeatability relative standard deviation values ranged from 2.2 to 4.6% and reproducibility standard deviation values ranged from 4.8 to 10.3%. The detection limits were 0.005-0.01 microgram/g. These results show the notified analytical method has good performance.

[Constituents of the petroleum ether and ethyl acetate extract fractions from Dracaena cochinensis (Lour.) S.C. Chen].

Six constituents have been isolated from the petroleum ether and ethyl acetate extract fractions of Dracaena cochinensis. Their structures have been identified as 1,2,4,5-tetrachloro-3,6- dimethoxy-benzene,docosyl alcohol, octadecyl acetate, eicosyl acetate, resveratrol and 4',7-dihydroxy-flavone on the basis of physical, chemical and spectral deta. Of these compounds 1,2,4,5-tetrachloro-3,6-dimethoxy-benzene is a new one.

[Polychlorinated biphenyls (PCBs) and polychlorinated quaterphenyls (PCQs) concentrations in skin surface lipids and blood of patients with Yusho].

The relationship between Polychlorinated Biphenyls (PCBs), and Polychlorinated Quaterphenyls (PCQs) concentrations in the skin surface lipids and blood was investigated in twenty two patients with PCB poisoning (Yusho) and 9 control subjects were analyzed. The collection of skin surface lipids was performed by the method of cotton pad with 70% ethyl alcohol. The alkaline decomposition method described as "the official standard analytical methods for the isolation of PCBs and PCQs fractions" was used. In the blood of control group, the mean value of PCBs concentration was 1.8 ng/g, and that of PCQs concentration was very low and undetectable by our analytical method. On the other hand, the PCBs concentration in the Yusho group was three times higher than those in the control group. The mean value of PCQs concentration was 1.90 ng/g in Yusho group, while it was not detectable in the control group. In the skin surface lipids of patients with Yusho, the mean value of PCBs concentration was 668.6 ng/g, but was 256.7 ng/g in the control group. The mean value of PCQs concentration in the skin surface lipids of Yusho patients was 35.4 ng/g, although it was not detected in the control group. These values of the skin surface lipids in 1993 were decreased as compared with those in 1992. PCBs and PCQs levels in the skin surface lipids were higher than those in the blood. These findings suggests that cutaneous sebaceous system is one of the excretory systems of polyhalogenated chemicals, such as PCBs or PCQs, when these chemicals are precipitated in human or mammalian.

Terrestrial physical and chemical processes for liquid waste treatment.

Experiences gained from full-scale evaluation of advanced treatment processes used for reclaiming wastewaters should help in the evaluation of potential treatment systems for treatment and reuse of water in space. Water Factory 21 is a 0.66 m3 s-1 (15 million gallons per day) water reclamation plant in California that has been in operation since 1976. The plant receives biologically treated wastewater. Lime treatment is effective for removal of heavy metals. Volatile organic constitutes are efficiently removed by air stripping. Non-volatile organic constituents are removed by activated carbon adsorption and reverse osmosis (RO). RO is a highly effective polishing step, and removes most of the remaining materials including inorganic salts, heavy metals, and organics. RO removed 85% of the total organic carbon, down to about 1 mg l-1, which is lower than in many treated drinking waters. The series of treatment processes used insured virus and pathogen removal, with lime treatment and chlorination together proving highly effective. Sufficient data has been collected to provide statistically reliable confidence limits to be set on the performance of each unit process.

[Studies on the application of residual PCBs, PCQs and PCDFs concentrations to Yusho diagnosis].

Results of Yusho annual inspection were reviewed from the view point of correlation of PCBs, PCQs and PCDFs concentration in blood or subcutaneous adipose tissue and clinical findings. To make discussion quantitative, fifteen terms of clinical findings on Yusho disease were quantified on the severity by evaluating (+) as 2 points, (+-) as 1 point and (-) as 0 point. First, the temporal variations of the severity of clinical findings on 5 Yusho patients were figured. Additionally, the temporal variations of blood triglyceride and PCBs concentration, and GOT were also surveyed. The adopted terms of clinical findings were general malaise, cough, sputum, headache, abdominal pain, peripheral neuropathy, soreness of joints, deformity of nails, comedo formation, acne-like eruption, secondary infection, scar formation, disorder of Meibomian glands, edema of eye lids and increased discharge from the eyes. During the investigated period from 1972 to 1988 the total score of clinical findings clearly decreased on two patients who had high score, tended to decrease on two other patients, and was not clear on another patient. Secondly, the correlation coefficients were calculated between each of PCDFs, PCBs or PCQs concentration in subcutaneous adipose tissue or blood and the total score at the year in which the adipose tissue and blood were taken. For the female patients the correlation coefficient of PCDFs concentration in subcutaneous adipose tissue and total score of clinical findings was the highest of all (r = 0.9885). However, for the male patients it was not available because the number of the subjects was only two. Thus far it has been reported that the powers of PCBs gas chromatogram pattern and PCQs concentration as criteria for Yusho diagnosis are low as for the subjects who belonged to the border area between Yusho patients and normal persons. This survey suggests that PCDFs concentration in subcutaneous adipose tissue can be a potent criterion that has a high correlation with the clinical findings of Yusho.

A comparative study on the concentrations of polychlorinated biphenyls (PCBs) and polychlorinated quaterphenyls (PCQs) in the blood and hair of "Yusho" patients and inhabitants of Nagasaki Prefecture.

The relationship between polychlorinated biphenyl (PCB) and polychlorinated quaterphenyl (PCQ) concentrations in the blood and hair was investigated. The materials in this study consisted of 49 blood samples and hair obtained from 27 patients with PCB poisoning (Yusho) and 22 normal controls. The alkaline decomposition method described in the official standard analytical methods for the isolation of PCB and PCQ fractions was used. In the blood of the control group, the mean concentration of PCBs was 2.25 ppb, while the concentration of PCQs was too low to be detected by our analytical method. On the other hand, the mean concentration of PCBs in the Yusho group was about 2.8 times higher than that in the control group. The mean concentration of PCQs in the blood was 0.61 ppb in the Yusho group, but PCQs were not detectable in the control group. In the hair, the mean concentration of PCBs was 25.85 ppb and 9.41 ppb in the Yusho group and control group respectively. The mean concentration of PCQs in the hair of Yusho patients was 0.44 ppb, but PCQs were not detected in the control group. The PCB level in the hair was higher than that in the blood, but the PCQ level in the hair was lower than that in the blood. These results suggest a difference of excretory system among polyhalogenated compounds such as PCBs or PCQs. We consider that PCBs display a greater affinity than PCQs for the pilosebaceous system of the human skin.(ABSTRACT TRUNCATED AT 250 WORDS)

A comparative study on polychlorinated biphenyls (PCB) and polychlorinated quaterphenyls (PCQ) concentrations in subcutaneous fat tissue, blood and hair of patients with yusho and normal control in Nagasaki prefecture.

The relationship between PCB and PCQ concentrations in the blood, subcutaneous fat tissue and hair was investigated in this study. PCB and PCQ concentrations in twenty four patients with PCB poisoning (yusho) and 59 normal controls were analyzed. The alkaline decomposition method described in the official standard analytical methods for the isolation of PCB and PCQ fractions was used. The mean value of PCB concentrations was 2.43 ppb, CB% ratio was 0.69 and the PCQ concentration in the blood of the control group was too low to be detected by our analysis. On the other hand, the PCB concentration and CB% ratio in the yusho group were two times higher than those in the control group. The mean value of PCQ concentration was 1.34 ppb in the yusho group although it was below the level of detection in the control group. The mean PCB concentration in the hair of patients with yusho was 28.92 ppb, and 8.06 ppb in the control group. CB% ratio in the hair of patients with yusho was two times higher than that in the control group. The mean value of PCQ concentration in the hair of patients with yusho was 0.55 ppb although it was not detected in the control group. The PCB and PCQ concentrations in the hair were not greatly elevated when compared with those in the subcutaneous fat tissue. However, the hair is an excellent sample for the detection of these chemicals because it can be collected simply without operation.