Formaldehyde Exposure in a Gross Anatomy Laboratory. Personal Exposure Level Is Higher Than Indoor Concentration (5 pp)

Goal, Scope and Background Cadavers for gross anatomy laboratories are usually prepared by using embalming fluid which contains formaldehyde (FA) as a principal component. During the process of dissection, FA vapors are emitted from the cadavers, resulting in the exposure of medical students and their instructors to elevated levels of FA in the laboratory. The American Conference of Governmental Industrial Hygienists (ACGIH) has set a ceiling limit for FA at 0.3 ppm. In Japan, the Ministry of Health, Labour and Welfare has set an air quality guideline defining two limit values for environmental exposure to FA: 0.08 ppm as an average for general workplaces and 0.25 ppm for specific workplaces such as an FA factory. Although there are many reports on indoor FA concentrations in gross anatomy laboratories, only a few reports have described personal FA exposure levels. The purpose of the present study was to clarify personal exposure levels as well as indoor FA concentrations in our laboratory in order to investigate the relationship between them. Methods The gross anatomy laboratory was evaluated in the 4th, 10th and 18th sessions of 20 laboratory sessions in total over a period of 10 weeks. Air samples were collected using a diffusive sampling device for organic carbonyl compounds. Area samples were taken in the center and four corners of the laboratory during the entire time of each session (4-6 hours). Personal samples were collected from instructors and students using a sampling device pinned on each person's lapel, and they were 1.1 to 6 hours in duration. Analysis was carried out using high performance liquid chromatography. Results and Discussion Room averages of FA concentrations were 0.45, 0.38 and 0.68 ppm for the 4th, 10th and 18th sessions, respectively, ranging from 0.23 to 1.03 ppm. These levels were comparable to or relatively lower than the levels reported previously, but were still higher than the guideline limit for specific workplaces in Japan and the ACGIH ceiling limit. The indoor FA concentrations varied depending on the contents of laboratory sessions and seemed to increase when body cavity or deep structures were being dissected. In all sessions but the 4th, FA levels at the center of the room were higher than those in the corners. This might be related to the arrangement of air supply diffusers and return grills. However, it cannot be ruled out that FA levels in the corners were lowered by leakage of FA through the doors and windows. Average personal exposure levels were 0.80, 0.45 and 0.51 ppm for instructors and 1.02, 1.08 and 0.89 ppm for students for the 4th, 10th and 18th session, respectively. The exposure levels of students were significantly higher than the mean indoor FA concentrations in the 4th and 10th sessions, and the same tendency was also observed in the 18th session. The personal exposure level of instructors was also significantly higher than the indoor FA level in the 4th session, while they were almost the same in the 10th and 18th sessions. Differences in behavior during the sessions might reflect the differential personal exposure levels between students and instructors. Conclusion The present study revealed that, if a person is close to the cadavers during the gross anatomy laboratory, his/her personal exposure level is possibly 2 to 3-fold higher than the mean indoor FA concentration. This should be considered in the risk assessment of FA in gross anatomy laboratories. Recommendation and Outlook If the risk of FA in gross anatomy laboratories is assessed based on the indoor FA levels, the possibility that personal exposure levels are 2 to 3-fold higher than the mean indoor FA level should be taken into account. Otherwise, the risk should be assessed based on the personal exposure levels. However, it is hard to measure everyone's exposure level. Therefore, further studies are necessary to develop a method of personal exposure assessment from the indoor FA concentration.     

AOX Formation and Elimination in the Oxidative Treatment of Synthetic Wastewaters in a UV-Free Surface Reactor (6 pp)

Intention, Goal, Scope, Background The effect of chloride concentration and pH on the UV oxidation systems was examined. Phenol and methanol were used as organic substances. The treatment of these chemicals by UV oxidation using a newly developed lab scale pretest UV-Free Surface Reactor (UV-FSR) with and without Cl– addition at different pH values, is evaluated. Results of this study indicated that the Cl– concentration of the water and the chemical structure of the substances is more important than the pH of the water. There was no AOX at the beginning of the experiments, but a de-novo synthesis of AOX was observed during the batch experiments. This is caused by the high chloride content of the wastewaters. It can be supposed that OHradicals oxidize some chloride-ions to form chlorine, which further reacts with organic compounds. During the treatment, these AOX compounds which are produced from the beginning of the reaction are destroyed again. Evaluations of these experiments were done according to TOC and AOX results. Approximately 80% and 99% TOC removal efficiencies were obtained for the treatment of Phenol and Methanol-containing wastewaters, respectively. Objective In the literature, there are no relevant publications concerning the AOX formation of wastewater by wet oxidation- iron catalysed or by application of UV. For that reason, the main objectives of this study were: 1. to see the influence of chloride concentration and pH on the AOXde-novo formation with newly developed UV-Free Surface Reactor (UV-FSR), 2. to make a comparison of different AOPs, 3. to observe the effect of the chloride concentration on the TOC degradation efficiency, 4. to optimise reaction conditions. Methods In synthetic wastewaters, Methanol (CH3OH) and Phenol (C6H5 OH) are used as pollutants. The concentration of each substance was 1000 mg/l and COD values were calculated theoretically. The H2O2 addition was calculated according to the COD with a convenient stoichiometric factor (e.g. 1). During experiments, the pH was always kept constant with the addition of either 25% H2SO4 or 33% NaOH depending on the experimental conditions. Each substance was treated with the addition of 1000 mg/l Cl–, 10000 mg/l Cl– and without Cl– addition at pH 3, pH 7 and pH 10, respectively. NaCl was used as a Cl– source. Adsorbable Organic Halogenides (AOX) were determined using a TOX analyser (European Standard EN 1485 H 14, 1996). TOC measurements were carried out using an Elementar High TOC Analyzer equipped with an auto sampler. The H2O2 concentration was measured according to German Standard Methods (DIN 38409, Part 15, 1987). Results and Discussion The first step was to determine the effect of pH on the AOX formation in the process. Therefore, experiments were carried out at three different pHs: acidic (pH 3), neutral (pH 7) and basic (pH 10) conditions at a constant initial Methanol concentration of 1000 mg/l and a hydrogen peroxide concentration of 3185 mg/l (1 x stoichiometric). All results were evaluated according to applied pH. At these conditions, the amount of H2O2 (53 ml / 10 l) concentration was nearly zero after 1 hour batch treatment of Methanol. There was no AOX at the beginning of the experiments, but the AOX value increased after 6–18 min. At the end of 1 hour batch treatment this produced AOX was treated again. The maximum AOX production was obtained with the addition of 10000 mg/l Cl–, whereas there is no AOX production during the experiment when Cl– was not used. In all studies, however, TOC values decreased to almost zero after 1 hour batch treatment. After the experiments with Methanol, Phenol treatment was carried out at different pHs as a second experiment. pH was kept constant with the addition of either H2SO4 or NaOH depending on the experimental conditions. During experiments with Phenol, the colour of the water changed from colourless to a yellowish- red. After 1 hour treatment, the colour of the water was red. Therefore, these experiments were continued until the water became colourless again, and this took about 5 hours. Although there was no AOX at the beginning of the experiments, it increased after 30 min to 1 hour oxidation with the addition of 1000 mg/l Cl– and 10000 mg/l Cl–. There was no AOX production during the experiments when Cl– was not added. At the end of 5 hours of treatment, formed AOX was degraded and the TOC concentration decreased from 766 mg/l to approximately 200 mg/l. Conclusion. These experiments of this study showed that the effects of Cl– concentration of the water and the chemical structure of the substances is more than that of the pH on the AOX formation. During the batch experiments, a de-novo synthesis of AOX was observed very impressively due to the high chloride content of the wastewaters. It can be implied that OH-radicals oxidize some chloride-ions to form chlorine, which further reacts with organic compounds so that AOXde-novo is formed. At the end of the reaction times these AOX compounds are also destroyed. Recommendation and Outlook It is more cost effective to use these processes for only purposes such as toxicity reduction, enhancement of biodegradability, decolourisation and removal of micropollutants. However, the most important point is the optimization of the reaction conditions for the process of concern. The AOP applied can be used, for instance, for AOX reduction and TOC removal of industrial wastewaters.     

Accumulation and Chemical Fractionation of Heavy Metals in Andisols after a Different, 6-year Fertilization Management (8 pp)

Goal, Scope and Background Andisols are widespread in Japan and have some special properties such as high anion exchange capacity, low bulk density, and high organic matter content, which might influence the accumulation or chemical fractionation of heavy metals. However, few such data exist in Japanese andisols. The primary objective of this study was to investigate the distribution and chemical fractions of Cu, Zn, Ni, and Cr in the soil profiles and subsequently to assess their potential environmental hazard. Materials and Methods Soil samples were taken from a field experiment conducted on Japanese andisols, which had received either swine compost or chemical fertilizers for 6 years. Concentrations of Cu, Zn, Ni, and Cr were determined for all of the obtained extract solutions by ICP-AES. Results and Discussion Considerably higher total concentrations of Cu and Zn were observed in the top 20 cm layer of the compost-amended soil, relative to the unfertilized soil, while chemical fertilizers had little effect. Application of the swine compost increased the concentrations of Cu and Zn, but not Ni and Cr, in all fractions in the top 20 cm layer. The greatest increase in the organically bound fraction (OM) Cu and dilute acid-exchangeable fraction (DAEXCH) Zn was observed. This suggests that Cu and Zn are potentially bioavailable and mobile in the andisol profiles after 6-year consecutive applications of the swine compost. On the other hand, distribution of Cu, Zn, Ni and Cr among various soil fractions was generally unaffected by chemical fertilizers. Conclusions We observed that 6-year consecutive applications of the swine compost led to an increase in total metals of Cu and Zn, as well as their all-chemical fractions, in the top 20 cm soil layers. Potential hazard of heavy metals, especially of Cu and Zn, as a result of the use of swine compost on andisols, must be taken into account. Recommendations and Outlook The long-term effect of the accumulation of heavy metals, particularly Cu and Zn, in various plant tissues and soils, as well as their potential risk to surface water via runoff and groundwater via leaching, needs to be carefully considered. Further investigations in the long-term experiments are therefore necessary. - Abbreviations. EXCH, exchangeable fraction of metals; DAEXCH, dilute acid-exchangeable fraction of metals; FeMnOX, iron and manganese-oxide-bound fraction; OM, organically-bound fraction; RESD, residual fraction. COMPOST, SRNF, RANF, and CONTROL stand for compost (from swine wastes), slow-release nitrogen fertilizer (coated urea), readily available nitrogen fertilizer (including NH4-N, P, and K fertilizers), and no fertilizer application, respectively.     

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.