Human exposure and health risk of alpha-, beta-, gamma- and delta-hexachlorocyclohexane (HCHs) in Tianjin, China

The dynamic exposures to HCHs of individuals born between the years 1913 and 1993 in Tianjin have been simulated by connecting a fugacity model (IV) with a multimedia exposure model. Ingestion is the most important pathway for human beings to take up HCHs, and concentrations in the human body correlate with body weight changes. Accumulations of HCHs were derived assuming that the degradation in human body behaved linearly. The health risk of exposure to HCHs was measured using cancer risk and loss of life expectancy (LLE), and LLE was modified from its original definition to incorporate a dynamic calculation that takes variances in exposure into account. Monte-Carlo simulations were run to analyze the uncertainties of the model.     

Ultrasonic destruction of surfactants: application to industrial wastewaters.

This research focused on the use of sonication to destroy surfactants and surface tension properties in industrial wastewaters that affect traditional water treatment processes. We have investigated the sonochemical destruction of surfactants and a chelating agent to understand the release of metals from surfactants during sonication. In addition, the effects of physical properties of surfactants and the effect of ultrasonic frequency were investigated to gain an understanding of the factors affecting degradation. Sonochemical degradation of surfactants was observed to be more effective than nonsurfactant compounds. In addition, as the concentration is increased, the degradation rate constant does not decrease as significantly as with nonsurfactant compounds in the near-field acoustical processor reactor. The degradation of metal complexes is not as effective as in the absence of the metal. However, this is likely an artifact of the model complexing agent used. Surfactant metal complexes are expected to be faster, as they will accumulate at the hot bubble interface, significantly increasing ligand exchange kinetics and thus degradation of the complex.     

The influence of organic ligands on the retention of lead in soil

Organic acids are commonly produced and exuded by plant roots and soil microorganisms. Some of these organic compounds are effective chelating agents and have the potential to enhance metal mobility. The effect of citrate and salicylate on the leaching of lead in soil was investigated in a laboratory experiment. In short-term batch experiments, adsorption of lead to soil was slightly enhanced with increasing salicylate concentration (500-5000 microM) but decreased significantly in the presence of citrate. These observations suggested that citrate may enhance Pb leaching, but this was not observed in the column study. Soluble Pb in the presence and absence citrate or salicylate (up to 5000 microM) was added to soil columns at a moderate flow rate, but no Pb was observed to emerge from the soil in any of the soil columns. Rapid biodegradation of citrate in soil eliminated potential complexing ability. Breakthrough of Pb from soil was noted only when using small columns at high flow rates (>20 pore volumes per day). Under these conditions of physical and chemical non-equilibrium, citrate was not degraded and significantly enhanced Pb mobility. As in the batch adsorption experiments, the presence of salicylate reduced Pb leaching. Considering the extreme conditions required to induce Pb leaching, it is likely that Pb will remain relatively immobile in soil even in the presence of a strong complexing agent such as citrate.     

The degradation of endocrine disruptor di-n-butyl phthalate by UV irradiation: a photolysis and product study

The direct photolysis of an important endocrine disruptor compound, di-n-butyl phthalate (DBP), has been investigated under monochromatic UV irradiation at 254 nm over a wide pH range (3-11). The investigation was carried out under idealized conditions and has considered both reaction kinetics and the degradation mechanism. It was found that more than 90% of DBP can be degraded within an hour of irradiation in water. A simple model has been developed and used to predict the initial DBP photolysis rate constant at different pH values and initial DBP concentrations. The major decomposition mechanism of DBP is believed to involve the hydrolytic photolysis of the carbon in the alpha and/or beta-position of the ester chain with the production of aromatic carboxylic derivatives. Additionally, multi-degradation pathways are proposed for acid-catalyzed hydrolytic photolysis (pH 3-5), which was found to be useful in explaining the photo-degradation of DBP under acidic conditions. The use of 254 nm UV to photo-degrade DBP was found to be a relatively fast and clean process, especially in neutral to basic conditions.     

Effects of a mixture of tetracyclines to Lemna gibba and Myriophyllum sibiricum evaluated in aquatic microcosms

The impact of a mixture of oxytetracycline, chlortetracycline, tetracycline and doxycycline on Myriophyllum sibiricum and Lemna gibba was investigated using fifteen 12,000-L microcosms (k=5, n=3). Significant concentration-response relationships were only found for M. sibiricum, where dry mass was 69, 47, 30, and 7% of controls at respective treatment concentrations of 0.080, 0.218, 0.668, and 2.289 micromol/L. Somatic endpoints were strongly and negatively correlated with percent light transmission, except plant length, which was positively correlated. Treated microcosms experienced a reduction in the percent of surface irradiance penetrating the water column as high as 99.8% at a depth of 70 cm, relative to controls. Position relative to the water column was likely responsible for the differential effects observed between floating (L. gibba) and submerged (M. sibiricum) species of macrophytes. A hazard quotient assessment of the lowest EC10 value indicated significant risk, exceeding the critical HQ value, but not the lowest EC25 value.     

Possibilities for improving nitrogen use from organic materials in agricultural cropping systems

Nitrogen release from organic nutrient sources in soil is influenced by a range of factors such as soil temperature and moisture, and chemical composition of the organic material. Chemical composition can, to a certain degree, be controlled to increase the synchronization of nitrogen (N) release with plant N demand, whereas climatic factors cannot be controlled and so must be taken into account when planning management measures. In this paper, we discuss different ways to affect N release through manipulation of the chemical composition of fresh or pretreated plant materials and animal manures, timing of incorporation, and intentional distribution during application. We conclude by giving an overview of off-farm options that may need to be implemented to achieve improved use of N, especially in agricultural systems with surplus N.     

Photocatalytic degradation of gaseous perchloroethylene: products and pathway

Batch photocatalytic degradation of 1000-ppm gaseous perchloroethylene (PCE) was conducted with UV irradiation such that nearly 100% was decomposed within 10 min. The main intermediate and final product were identified as trichloroacetylchloride (TCAC) and hydrogen chloride (HCl), respectively, and minor ones as dichloroacetic acid (DCAC), monochloroacetic acid (MCAC), carbon tetrachloride, chloroform, and phosgene. More than 90% of Cl- equivalent, i.e., the sum of the chlorine number in PCE, intermediates, and HCl, was compensated for during the time of PCE degradation; a result indicating that no other major chlorinated intermediates are present during the time of PCE degradation. In a similar experiment, 500 ppm of gaseous TCAC degraded into HCl within 3 h without producing DCAC or MCAC, where like PCE, more than 90% of Cl- equivalent, i.e., the sum of the chlorine number in TCAC and HCl, was compensated for during time of TCAC degradation. Accordingly, gaseous PCE is concluded to predominantly follow a degradation pathway of PCE --> TCAC --> HCl.     

Evaluating non-equilibrium solute transport in small soil columns

Displacement studies on leaching of bromide and two pesticides (atrazine and isoproturon) were conducted under unsaturated steady state flow conditions in 24 small undisturbed soil columns (5.7 cm in diameter and 10 cm long) each collected from two sites differing in soil structure and organic carbon content in North Germany. There were large and irregular variabilities in the characteristics of both soils, as well as in the shapes of breakthrough curves (BTCs) of different columns, including some with early breakthrough and increased tailing, qualitatively indicating the presence of preferential flow. It was estimated that one preferential flow column (PFC) at site A, and four at site B, contributed, respectively to 11% and 58% of the accumulated leached fraction and to more than 80% of the maximum observed standard deviation (SD) in the field-scale concentration and mass flux of pesticides at two sites. The bromide BTCs of two sites were analyzed with the equilibrium convection-dispersion equation (CDE) and a non-equilibrium two-region/mobile-immobile model. Transport parameters of these models for individual BTCs were determined using a curve fitting program, CXTFIT, and by the time moment method. For the CDE based equilibrium model, the mean values of retardation factor, R, considered separately for all columns, PFCs or non-preferential flow columns (NPFCs) were comparable for the two methods; significant differences were observed in the values of dispersion coefficients of two sites using the two estimation methods. It was inferred from the estimated parameters of non-equilibrium model that 5-12% of water at site A, and 12% at site B, was immobile during displacement in NPFCs. The corresponding values for PFCs of two sites were much larger, ranging from 25% to 51% by CXTFIT and from 24% to 72% by the moment method, suggesting the role of certain mechanisms other than immobile water in higher degrees of non-equilibrium in these columns. Peclet numbers in PFCs of both sites were consistently smaller than five, indicating the inadequacy of the non-equilibrium model to incorporate the effect of all forms of non-equilibrium in PFCs. Overall, the BTCs of individual NPFCs, PFCs and of field average concentration at the two sites were better reproduced with parameters obtained from CXTFIT than by the moment method. The moment method failed to capture the peak concentrations in PFCs, but tended to describe the desorption and tail branches of BTCs better than the curve fitting approach.     

Oxidation of triphenylarsine to triphenylarsineoxide by Trichoderma harzianum and other fungi

Arsenic resistant strains of bacteria and fungi were isolated from soil contaminated by chemical warfare agents. Until now, no metabolic products of microbial attack against the phenyl residues of the model substrate triphenylarsine (TP) were found if it was incubated together with these strains in liquid culture assays. However, one of the isolated fungi, Trichoderma harzianum As 11, was found to oxidize TP to triphenylarsineoxide (TPO). The yeast Trichosporon mucoides SBUG 801 and the white-rot fungus Phanerochaete chrysosporium were also able to oxidize the As(III) in TP. In addition, P. chrysosporium transformed phenylarsineoxide (PAO) to phenylarsonic acid (PAA) under O2-atmosphere. By means of a respirometer system, the oxidation of TP by T. harzianum As 11 was confirmed by a significantly higher consumption of oxygen in the presence of these compounds. HPLC analysis of the oxidation products TPO and PAA in the medium of the assays provided evidence for the transfer reaction of As(III) to As(V) in organic bonds. The oxidation products TPO and PAA are more hydrophilic than TP and PAO. Therefore, it was concluded that particular fungi contribute to the mobilization of arsenic in soil contaminated by chemical warfare agents.     

Insecticide residues in cotton crop soil

Dimethoate, monocrotophos, triazophos, deltamethrin, cypermethrin and endosulfan were applied to a cotton crop soil located at Nurpur village, Punjab, India. The insecticides were applied sequentially at recommended dosages in cotton fields by foliar application in 1995, 1996 and 1998. Soil samples were collected from the cotton crop farms and extracted with acetone. The extracted material was analysed by a gas liquid chromatograph (GLC) equipped with an 63Ni electron-capture detector (ECD-63Ni). Recovery data was obtained by fortifying soil with insecticide. The average recoveries from the fortified soil samples were 76-92% for organophosphorous compounds and 90-98% for synthetic pyrethroids and organochlorines. The results showed that the insecticide residues under study were present in the range of 1.16 to 41.97 ng g(-1) d.wt.soil. The pattern of dissipation of the insecticides used was similar for the duration of the crop. Half lives of the insecticides ranged from 7 to 22 days. Except endosulfan none of the other insecticides used were leached below 15 cm. Endosulfan was found to be rapidly degraded in the soil and formed a sulfate metabolite. Persistence and dissipation pattern in soils with history of exposure to the insecticide compared to non-history soils were similar.