QSAR study on the toxicity of substituted benzenes to the algae (Scenedesmus obliquus).

50% effective inhibition concentration 48h-EC50 of 40 substituted benzenes to the algae (Scenedesmus obliquus) was determined. The energy of the lowest unoccupied molecular orbital (E(LUMO)) was calculated by the quantum chemical method MOPAC6.0-AM1. By using E(LUMO) and the hydrophobicity parameter log K(OW) the quantitative structure-activity relationship model (QSAR) was developed: log1/EC50=0.272 logK(OW) - 0.659E(LUMO) + 2.54, R2 = 0.793, S.E. = 0.316, F = 71.07, n = 40. A series of equations were obtained about the measured EC50 values of different subclasses of compounds. For those compounds containing double -NO2, their toxicity may be related chiefly to the intracellular reduction of -NO2 obtaining electron, while for anilines and phenols, K(OW) contributes most to the QSAR and E(LUMO) very little.     

EVALUATING POTENTIAL ENVIRONMENTAL IMPACT OF INSECTICIDE APPLICATIONS IN A BOLL WEEVIL ERADICATION PROGRAM1

ABSTRACT: Concerns have been expressed about the potential insecticide contamination of regional water resources from a boll weevil eradication program in Oklahoma. A mathematical model and geographic information system techniques were utilized to evaluate the potential of insecticide leaching and runoff from a major proposed program area in the state. Different but equally likely weather patterns were generated, and potential insecticide losses associated with each pattern were predicted. Soil types and their locations within cotton areas were identified, and potential chemical losses from each soil were delineated. Model simulations indicated that azinphos-methyl and diflubenzuron could leach from some porous soils and that all insecticides suggested for use in the program could be lost to runoff. The predicted chemical movements with runoff were significantly higher on irrigated land than from non-irrigated land. Malathion demonstrated no leaching and low potential of runoff losses among the insecticides evaluated.     

Prediction of fish bioconcentration factors of nonpolar organic pollutants based on molecular connectivity indices.

The relationship between bioconcentration factors and molecular connectivity indices was investigated. A regression model was developed using 80 measured BCFs of nonpolar organic pollutants. The five topological parameters used were 1 chi, 2 chi, 3 chi c, 0 chi v and 2 chi v. Modified jackknife tests were applied to examine the robustness of the model by repeatedly removing a set of or a class of compounds from the database. The model was compared with one using Kow as an independent parameter. The mean absolute errors for the 80 compounds studied were 0.288 and 0.302 log-unit for the two models, respectively.     

Speciation and preservation of inorganic arsenic in drinking water sources using EDTA with IC separation and ICP-MS detection

The native distribution of As(III) and As(v) in drinking water supplies can influence the treatment removal strategy. The stability of As(III) and As(v) in iron-rich drinking waters can be affected by the formation of Fe precipitates (Fe oxides and/or hydroxides designated by "FeOOH"). These precipitates (ppts) can form during the transport of the sample to the laboratory for arsenic speciation analysis. The analysis of the ppt indicates considerable loss of the aqueous arsenic species (As(aq)) to the solid phase "FeOOH" ppt. Studies of laboratory reagent water containing both As(III) and Fe(III) indicate that the resulting "FeOOH" ppt contained a mixture of As(III) and As(v) with near quantitative removal of the As(aq) in 18 hr. The corresponding aqueous fraction after filtration through a 0.45 microm filter was composed primarily of As(v). The formation of "FeOOH" ppt and the loss of As(aq) to the ppt can be virtually eliminated by the use of EDTA, which sequesters the FeIII). Reagent water fortified with Fe(III), As(III) and EDTA produced less than a 1 ppb change in the As(III)aq concentration over 16 d. The EDTA treatment was also tested on three well waters with different native As(III )/As(v) ratios. The native distribution of As(III)/As(v) was stabilized over a period of 10 d with a worst case conversion of As(III) to As(v) of 2 ppb over a 30 d period. All well waters not treated with EDTA had dramatic losses (a factor of 2-5) of As(aq) in less than 1 d. These results indicated that EDTA preservation treatment can be used to preserve As(aq) in waters where the predominant species is the reduced form [As(III)] or in waters which the predominant species is the oxidized form [As(v)]. This preliminary investigation of EDTA to preserve As species in Fe-rich waters indicates stability can be achieved for greater than 14 d.     

Formation of a Mercury Plated Carbon Paste Electrode by Electroreduction of a Mercury(II) Diethyldithiocarbamate Modified Carbon Paste

A novel approach to formation of a mercury film electrode (MFE) at the surface of a carbon paste electrode is proposed in this paper. This MFE is easy to fabricate, has good reproducibility and avoids the use of a plating mercury solution. In this new type of MFE, mercuric diethyldithiocarbamate (Hg(DDTC)2) was mixed with graphite powder and paraffin oil to form a chemically modified carbon paste electrode. When a -0.95V potential was applied to the electrode, the Hg(II) (in Hg(DDTC)2) was reduced to metallic Hg, thus forming a mercury film at the surface of the carbon paste electrode. The characteristics of this MFE were studied. This modified electrode was used in anodic stripping voltammetry. Conditions for the simultaneous determination of trace amount of Pb(II) and Cd(II) were also investigated.     

Continuous flow methods for evaluating the response of a copper ion selective electrode to total and free copper in seawater

This work describes the development of an instrument for measuring free and total copper in seawater by continuous flow analysis (CFA) with an Orion copper (II) ion selective electrode (CuISE). Sample analysis times are reduced considerably by using an extrapolation technique based on the fitting of an empirical mathematical expression to the electrode time-response curve enabling a prediction of the final equilibrium potential. CuISE measurements in seawater samples containing nanomolar levels of total copper can be very time consuming, and this predictive approach significantly reduces sample analysis time, and improves sample throughput. The time taken to measure pCu in seawater to a precision of +/- 0.1, using conventional potentiometry, varies considerably depending on the condition of the electrode membrane but can be reduced by a factor of 3-6 (typically from 60 to 10 min) by using the extrapolation technique in conjunction with CFA. Details are given of the protocols used for preconditioning the CuISE. The system can be used as a portable instrument for field measurements or for shipboard measurements of free copper in seawater. Extrapolated equilibrium potentials are within +/- 0.5 mV of true steady state values.     

A conductive polypyrrole based ammonium ion selective electrode

In view of the development of miniaturized sensor arrays, a solid-contact ammonium ion selective electrode has been investigated. A conductive polypyrrole film was electrochemicallydeposited on a glassy carbon surface and used as an internal solid contact layer between the sensing membrane and solid electrode surface. A systematic evaluation of the importantparameters affecting the electromotive force (emf) response ispresented. The performances of this solid-contact sensor were verified using a batch-mode measurement setup and a wall-jet flow cell system. The designed sensor exhibited excellent selectivity for the primary ion and a linear response over the pNH₄ ⁺ range 1–5 with a slope of 56.3 mV decade^-1. The sensor has a fast response and is relativelyrobustness, and was also used to determine ammonium concentrations in natural waters, with promising results.     

Dissolved organic iodine in marine waters: role in the estuarine geochemistry of iodine

Non-volatile dissolved organic iodine (DOI) can be a major, or even the dominant, species of dissolved I in coastal, inshore and estuarine waters. It can be converted to IO3- in the presence of an oxidizing agent and to I- by reacting it with a reducing agent. Depending on the exact experimental conditions, the yields of these reactions may not be quantitative. In previous analytical schemes for the determination of IO3-, I- and DOI in marine waters, if oxidation or reduction steps are involved and the concentrations of one or more species are estimated by difference, the presence of DOI can lead to an overestimation of the concentrations of the inorganic species determined by difference and an underestimation of the concentration of DOI. In two cruises covering the James River to the southern Chesapeake Bay and from the southern Chesapeake Bay to the Atlantic, above a salinity (S) of 2, the contribution of DOI to total I increased with decreasing salinity and reached a maximum of 80%. DOI, I- and IO3- were successively the dominant form of dissolved I at 0.1 < S < 15 in the James River estuary, 15 < S < 30 in the Southern Chesapeake Bay and S > 30 in the Atlantic Ocean at the Bay mouth, respectively. Total I behaved conservatively (i.e., no evidence of consumption or production) during estuarine mixing during both cruises. In the southern Chesapeake Bay, total inorganic I was also approximately conservative. The primary process affecting the speciation of dissolved I was the conversion of IO3- to I-. In the James River estuary, there were indications of the conversion of both IO3- and I- to DOI. The concentrations of total I, IO3-, I- and DOI in James River water were 0.121, undetectable, 0.068 and 0.053 microM, respectively. These concentrations of total I and I- are significantly higher while that of IO3- is noticeably lower than those used presently for estimating global riverine input of these I species to the oceans. The riverine flux of DOI to the oceans is presently unknown.     

Photosynthetic acclimation and biochemical responses ofGelidium sesquipedale cultured in chemostats under different qualities of light

The red algaGelidium sesquipedale (Clem.) Born. et Thur. has been cultured in chemostats to assess the effects of light quality and photon-fluence rate (PFR) on growth, photosynthesis and biochemical composition. Plants under blue and red light (BL and RL) showed higher growth rates than under white light (WL) of the same PFR (40 mol m^–2 s^–1). The light-saturated rate of photosynthesis was higher for algae grown under BL and RL than for algae grown under WL. When algae were transferred to WL of moderate PFR (100 mol m^–2 s^–1), the light-saturated rate of photosynthesis decreased, being higher in previously RL-grown algae than in previously BL- and WL-grown algae. The initial slope of photosynthesis-irradiance (PI) curves () was affected by PFR but not by light quality. Pigment content was little affected by light quality. Light-quality treatments also affected the biochemical composition of the alga; previous exposure to various light treatments activate or repress several metabolical pathways that are fully expressed in the subsequent phase of WL of moderate PFR. Thus, phycobiliproteins and soluble proteins increased for previously BL- and RL-grown algae, whereas insoluble carbohydrate concentration was reduced, indicating a change of the C-partitioning between carbon compounds and organic nitrogen compounds. Inorganic nitrogen metabolism was also affected by light: under WL of moderate PFR, NO₃ ^– was totally depleted from sea water, and maximal values of NO₃ ^– uptake were recorded. In addition, neither NO₂ ^– nor NH₄ ⁺ was released. However, when algae were transferred to a low PFR, there was a drastic reduction of NO₃ ^– uptake under WL, which only partially recovered over time. It was accompanied by the release of NO₂ ^–, but not NH₄ ⁺, to the culture medium. Under BL and RL, however, there was a transient enhancement of NO₃ ^– uptake that was followed by a net release of NO₂ ^– and NH₄ ^–. Growth rates were not correlated with PFR. This could be due to the the dynamics of internal carbon mobilization and accumulation in the algae. When algae were exposed to a moderate PFR of WL, carbon requirements for growth were satisfied by photosynthesis. Thus, there was a net accumulation of carbon in the tissue. In contrast, when algae were exposed to low PFRs of either WL, BL or RL, observed growth rates could not be maintained by photosynthesis and carbon was mobilized.     

Persistent organic pollutants in source-separated compost and its feedstock materials--a review of field studies

Composting and the application of compost to the soil follow the principle of recycling and sustainability. Compost can also have a positive effect on physical, chemical, and biological soil parameters. However, little is known about the origin, concentration, and transformation of persistent organic pollutants (POPs) in compost. We therefore compiled literature data on some priority POPs in compost and its main feedstock materials from more than 60 reports. Our data evaluation suggests the following findings. First, median concentrations of Sigma 16 polycyclic aromatic hydrocarbons (PAHs), Sigma 6 polychlorinated biphenyls (PCBs), and Sigma 17 polychlorinated dibenzo-p-dioxins and -furans (PCDD/Fs) were higher in green waste (1803, 15.6 microg/kg dry wt., and 2.5 ng international toxicity equivalent [I-TEQ]/kg dry wt.) than in organic household waste (635, 14.6 microg/kg dry wt., and 2.2 ng I-TEQ/kg dry wt.) and kitchen waste (not available [NA], 14.9 microg/kg dry wt., 0.4 ng I-TEQ/kg dry wt.). The POP concentrations in foliage were up to 12 times higher than in other feedstock materials. Second, in contrast, compost from organic household waste and green waste contained similar amounts of Sigma 16 PAHs, Sigma 6 PCBs, and Sigma 17 PCDD/Fs (1915, 39.8 microg/kg dry wt., and 9.5 ng I-TEQ/kg dry wt., and 1715, 30.6 microg/kg dry wt., and 8.5 ng I-TEQ/kg dry wt., respectively). Third, concentrations of three-ring PAHs were reduced during the composting process, whereas five- to six-ring PAHs and Sigma 6 PCBs increased by roughly a factor of two due to mass reduction during composting. Sigma 17 PCDD/Fs had accumulated by up to a factor of 14. Fourth, urban feedstock and compost had higher POP concentrations than rural material. Fifth, the highest concentrations of POPs were usually observed in summer samples. Finally, median compost concentrations of POPs were greater by up to one order of magnitude than in arable soils, as the primary recipients of compost, but were well within the range of many urban soils. In conclusion, this work provides a basis for the further improvement of composting and for future risk assessments of compost application.