An analytical method to determine Henry's law constant for selected volatile organic compounds at concentrations and temperatures corresponding to tap water use

Henry's law constants (H) are needed to model human exposure to Volatile Organic Compounds (VOCs) in indoor air resulting from the use of tap water. This paper presents an experimental method to determine Hs for several common tap water pollutants at concentrations and temperatures used in household water. For 5 VOCs Henry's law constants were obtained simultaneously over the 25 degrees C to 45 degrees C temperature range, providing data on H beyond the currently available data (up to 35 degrees C). Henry's law constants were obtained as the ratio of equilibrium concentrations of VOCs in air and water, using simultaneous sampling from sealed bottles kept at constant temperatures. Air and water samples were concentrated by a purge-and-trap method, thermally desorbed from a Tenax trap, and analyzed with a gas chromatograph with an electron capture detector (GC-ECD). Experimental results agreed well with available literature data.     

The Role of a Salt Marsh Plant on Trace Metal Bioavailability in Sediments. Estimation By Different Chemical Approaches * (7 pp)

Goal, Scope and Background The presence or absence of vegetation can condition sediment characteristics. The main aim of this work was to investigate the influence of the sea rush Juncus maritimus on metal (Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn) availability to organisms living on or in estuarine sediments, from Douro River (NW Portugal), by comparing the characteristics and chemical behaviour of rhizosediments (collected within the plant assemblage) and those of sediment (collected around the plant). In order to evaluate whether and how sediment characteristics condition the role of plants on metal availability, sandy and muddy sediments colonised by J. maritimus were studied in parallel. Methods Metal availability was estimated by enzymatic digestion with pepsin (ED), which may provide an estimate of metal availability to organisms living at estuarine sediments. Nevertheless, since no consensus exists yet on the most suitable methodologies to estimate metal bioavailability in sediments, two more conventional approaches, BCR sequential extraction (SE) and AVS/SEM model, were also used, in parallel, and the information these approaches provided was compared with that provided by ED. Total-recoverable metal contents were determined by atomic absorption spectrophotometry after sediment digestion using a high-pressure microwave system. Results and Discussion Plants could concentrate metals around its roots and rhizomes. In addition, they were capable of oxidizing (release of oxygen by the roots) the anaerobic medium surrounding their roots in muddy sediment (reducing AVS). As sulphide oxidation renders metals (Cd, Cu, Ni, Pb and Zn) into more soluble forms, according to the AVS/SEM model, metals from muddy sites would be more available in rhizosediment than in sediment. The SE approach led to a similar conclusion. Nevertheless, the results provided by ED pointed at opposite conclusion, particularly for Cd and Zn, indicating less availability at rhizosediments than in the surrounding sediment. ED results were interpreted as a consequence of an enrichment of the rhizosediment in organic ligands exuded by the roots or liberated by dead plants. The effect of complexation of metals by organic compounds, which ED could not decompose/dissolve, seemed to overcome that caused by sediment oxidation. In general, a comparison of the information about metal availability by ED, SE, AVS/SEM, showed that it did not always match and in few cases it was even contradictory. Conclusion and Outlook Therefore, a thorough evaluation of the metal availability in sediments requires a combination of different chemical approaches, so as to take into consideration differences in ways of organism exposure (interstitial water and/or ingestion of sediment particles). - * The basis of this peer-reviewed paper is a presentation at the 9th FECS Conference on 'Chemistry and Environment', 29 August to 1 September 2004, Bordeaux, France.     

The effects of land use change on mercury distribution in soils of Alta Floresta, Southern Amazon

This study presents the spatial distribution, degree of contamination and storage capacity of Hg in surface forest and pasture soils from Alta Floresta, Southern Amazon, a significant gold mining site from 1980 to 1996. During that period, average annual gold production was about 6.5 tons, with an estimated Hg annual emission to the environment of about 8.8 tons, 60-80% of it being emitted to the atmosphere. Mercury sources to the region are mining sites and gold-dealer shops at the city of Alta Floresta, where gold is smelted and commercialized. Mercury concentrations in forest soils (15-248 ng g(-1), average=61.9 ng g(-1)) were 1.5-3.0 times higher than in pasture soils (10-74 ng g(-1), average=33.8 ng g(-1)), suggesting strong re-mobilization after deforestation. Highest Hg concentrations were found within a distance of 20-30 km from mining sites in both soil types. The influence of the refining operations within the city of Alta Floresta, however, was less clear. Somewhat higher concentrations were observed only within a 5 km radius from the city center where gold-dealer shops are located. Wind direction controls the spatial distribution of Hg. Background concentrations (15-50 ng g(-1)) were generally found at the outer perimeter of the sampling grid, about 40 km from sources. This suggests that Hg released from mining and refining activities undergoes rapid deposition. Estimated cumulative Hg burdens for the first 10 cm of soil averaged 8.3 mg m(-2) and 4.9 mg m(-2), for forest and pasture soils respectively and compare well with ultisols and hydromorphic oxisols, but were lower than those found in yellow-red and yellow latosols and podsols from other Amazonian areas. Our results show that changing land use in the Amazon is a strong re-mobilizing agent of Hg deposited on soils from the atmosphere.     

Cadmium uptake and translocation in tumbleweed (Salsola kali), a potential Cd-hyperaccumulator desert plant species: ICP/OES and XAS studies

Cadmium is a heavy metal, which, even at low concentrations, can be highly toxic to the growth and development of both plants and animals. Plant species vary extensively in their tolerance to excess cadmium in a growth medium and very few cadmium-tolerant species have been identified. In this study, tumbleweed plants (Salsola kali) grown in an agar-based medium with 20 mgl(-1) of Cd(II) did not show phytotoxicity, and their roots had the most biomass (4.5 mg) (P < 0.05) compared to the control plants (2.7 mg) as well as other treated plants. These plants accumulated 2696, 2075, and 2016 mg Cd kg(-1) of dry roots, stems, and leaves, respectively. The results suggest that there is no restricted cadmium movement in tumbleweed plants. In addition, the amount of Cd found in the dry leaf tissue suggests that tumbleweed could be considered as potential cadmium hyperaccumulating species. X-ray absorption spectroscopy studies demonstrated that in roots, cadmium was bound to oxygen while in stems and leaves, the metal was attached to oxygen and sulfur groups. This might imply that some small organic acids are responsible for Cd transport from roots to stems and leaves. In addition, it might be possible that the plant synthesizes phytochelatins in the stems, later coordinating the absorbed cadmium for transport and storage in cell structures. Thus, it is possible that in the leaves, Cd either exists as a Cd-phytochelatin complex or bound to cell wall structures. Current studies are being performed in order to elucidate the proposed hypothesis.     

Field method comparison between passive air samplers and continuous monitors for Vocs and NO2 in El Paso, Texas

This study evaluates the performance of Model 3300 Ogawa Passive Nitrogen Dioxide (NO2) Samplers and 3M 3520 Organic Vapor Monitors (OVMs) by comparing integrated passive sampling concentrations to averaged hourly NO2 and volatile organic compound (VOC) measurements at two sites in El Paso, TX. Sampling periods were three time intervals (3-day weekend, 4-day weekday, and 7-day weekly) for three consecutive weeks. OVM concentrations were corrected for ambient pressure to account for higher elevation. Precise results (< 5% relative standard deviation, RSD) were found for NO2 measurements from collocated Ogawa samplers. Reproducibility was lower from duplicate OVMs for BTEX (benzene, toluene, ethylbenzene, and xylene isomers) VOCs (> or = 77% RSD for 2-day samples) with better precision for longer sampling periods. Comparison of Ogawa NO2 samplers with chemiluminescence measurements averaged over the same time period suggested potential calibration problems with the chemiluminescence analyzer. For BTEX species, generally good agreement was obtained between OVMs and automated-gas chromatograph (auto-GC) measurements. The OVMs successfully tracked increasing levels of VOCs recorded by the auto-GCs. However, except for toluene, OVM BTEX measurements generally exceeded their continuous counterparts with a mean bias of 5-10%. Although interpretation of the study results was limited due to small sample sizes, diffusion barrier influences caused by shelters that housed OVMs and differences in sampling heights between OVMs and auto-GC inlet may explain the overestimation.     

Organochlorine pesticides in the surface waters of Northern Greece

A survey undertaken in Northern Greece has shown that organochlorine pesticides are present in the surface waters. Surface water samples have been collected seasonally from four rivers and five lakes for a period of two years. Solid-phase extraction followed by gas chromatographic techniques with electron capture detection was used for the determination of the compounds. The most commonly encountered organochlorine pesticides in surface waters were the isomers of hexachlorocyclohexane, aldrin, dieldrin and endosulfan sulfate. In some cases the concentrations detected were higher than the qualitative target levels set by the European Union, especially for hexachlorocyclohexane and aldrin. The occurrence of these compounds in Greek surface waters can be attributed to intense agricultural activity as well as to transboundary pollution.     

In vitro EROD induction equivalency factors for the 10 PAHs generally monitored in risk assessment studies in The Netherlands

The ethoxy resorufin dealkylase (EROD) inducing potency of 10 polycyclic aromatic hydrocarbons (PAHs) is measured in the H4IIE in vitro bioassay and the results are compared to those reported in literature. The selected PAHs varied considerably in their potency to induce EROD activity. Anthracene (Ant) and phenanthrene (Phe) showed consistently no response. Naphthalene (Nap) showed no or a very weak response on EROD activity. Fluoranthene (Fla) and benzo[g,h,i]perylene (BghiP) showed weak responses at the highest doses. The other PAHs, including indeno[1,2,3-cd]pyrene (IP), benz[a]anthracene (BaA), benzo[a]pyrene (BaP), chrysene (Chr) and benzo[k]fluoranthene (BkF), showed full bell shaped dose-response curves. BaP EROD induction equivalency factors (BaP-1EF) were calculated and increased in the order Ant approximately Phe < Fla < Nap < BghiP < IP < BaA < BaP < Chr < BkF. Comparison of BaP-IEFs based on 50% effect concentration (EC50) or lowest effect concentration (LEC), yielded a significant relationship between both methods described by the equation log(BaPIEF(EC50) = 0.55 x log(BaPIEF(LEC)) + 0.07 (r2 = 0.913). BaP-IEFs as derived from our measurements and as reported in literature and measured in other in vitro assays deviated up to a factor of 17 among the different studies, but the potency rankings were comparable. For the PAH mixture as on average present in the human diet an overall tetrachlorodibenzo-p-dioxin (TCDD)-IEF of 1 x 10(-4) was estimated. The total PAH based TCDD induction equivalents (IEQ) intake then was calculated 300 pg/day, which is approximately 2 times higher then the PHAH based TCDD-EQ intake reported for humans.     

Water technology for specific water usage

BACKGROUND: Water is the basis for life and culture. In addition to the availability of water its quality has become a major issue in industrialized areas and in developing countries as well. Water usage has to be seen as part of the hydrological cycle. As a consequence water management has to be sustainable. The aim of the contribution is to give water usage oriented quality criteria and to focus on the technical means to achieve them. MAIN FEATURES: Water is used for many purposes, ranging from drinking and irrigation to a broad variety of technical processes. Most applications need specific hygienic, chemical and/or physical properties. RESULTS: To meet these demands separation and reaction principles are applied. The reuse of water and the application of water treatment with little or no waste and by-product formation is the way to go. Membrane separation and advanced oxidation including catalytic reactions are promising methods that apply natural processes in sustainable technical performance. Thus elimination of specific water constituents (e.g. salts and metals, microorganisms) and waste water cleaning (e.g. pollutants, nutrients and organic water) can be done efficiently. OUTLOOK: Learning from nature and helping nature with appropriate technology is a convincing strategy for sustainable water management.     

Hormetic effect of glyphosate on Urochloa decumbens plants

Abstract

Urochloa decumbens plants may be reached by herbicide drift from applications of glyphosate from neighboring areas or by variations during applications. Considering the different phenological stages and size of plants in these areas, the amount of active ingredient that reaches the plants probably varies. The objective of this study was to evaluate the effects of the application of different doses of glyphosate on U. decumbens plants. Two greenhouse experiments were conducted with two replications at different times. The first experiment evaluated the biological response of U. decumbens plants to glyphosate doses (0, 2.81, 5.63, 11.25, 22.5, 45, 90, 180, 360, 720, and 1,440?g a.e. ha^?1), with six replications. The second experiment evaluated the response of U. decumbens plants to the application of a selected low dose of 11.25?g a.e. ha^?1. Evaluations of injury were performed at 0, 7, 14, and 21?days after application, and dry weight of plants was determined for each evaluation period. U. decumbens plants increased in dry weight when using the glyphosate dose of 11.25?g a.e. ha^?1. However, plants had different responses to the application of this low dose. It can promote both stimulation and inhibition of plant growth.     

Formation of Nitrate and Sulfate in the Plume of Berlin (8 pp)

Background, Aims and Scope Secondary inorganic aerosol (SIA), i.e. particulate sulphate (S(VI)), ammonium and nitrate (N(V)) is formed from gaseous precursors i.e., sulfur dioxide (S(IV)), ammonia and nitrogen oxides, in polluted air on the time-scale of hours to days. Besides particulate ammonium and nitrate, the respective gaseous species ammonia and nitric acid can be formed, too. SIA contributes significantly to elevated levels of respirable particulate matter in urban areas and in strongly anthropogenically influenced air in general. Methods The near-ground aerosol chemical composition was studied at two stationary sites in the vicinity of Berlin during a field campaign in summer 1998. By means of analysis of the wind field, two episodes were identified which allow to study changes within individual air masses during transport i.e., a Lagrangian type of experiment, with one station being upwind and the other downwind of the city. By reference to a passive tracer (Na+) and estimates on dry depositional losses, the influences of dispersion and mixing on concentration changes can be eliminated from the data analysis. Results and Discussion Chemical changes in N(-III), N(V) and S(VI) species were observed. SIA i.e., N(V) and S(VI), was formed from emissions in the city within a few hours. The significance of emissions in the city was furthermore confirmed by missing SIA formation in the case of transport around the city. For the two episodes, SIA formation rates could be derived, albeit not more precise than by an order of magnitude. N(V) formation rates were between 1.4 and 20 and between 1.9 and 59 % h-1 on the two days, respectively, and S(VI) formation rates were > 17 and > 10 % h-1. The area south of the city was identified as a source of ammonia. Conclusion The probability of occurrence of situations during which the downwind site (50 km downwind of Berlin) would be hit by an urban plume is > 7.4%. Furthermore, for the general case of rural areas in Germany it is estimated that for more than half of these there is a significant probability to be hit by an urban plume (> 8%). The S(VI) formation rates are higher than explainable by homogeneous gas-phase chemistry and suggest the involvement of heterogeneous reactions of aerosol particles. Recommendation and Outlook The possible contribution of heterogeneous processes to S(VI) formation should be addressed in laboratory studies. Measurements at more than two sites could improve the potential of Lagrangian field experiments for the quantification of atmospheric chemical transformations, if a second downwind site is chosen in such a way that, at least under particular stability conditions, measurements there are representative for the source area.