Occupational exposure to fluorinated hydrocarbons during refrigeration repair work

This study describes refrigeration repair workers' occupational exposures to halogenated refrigerants, focusing on difluorochloromethane (HCFC 22), tetrafluoroethane (HFC 134a) and a mixture of tri-, tetra- and pentafluoroethane (R404A) in 30 work operations. Unlike earlier reported studies, the present study includes working procedures involving welding in order to measure possible occupational exposure to decomposition products. The measurements included hydrogen fluoride (HF), hydrogen chloride (HCl), phosgene (COCl2) and volatile organic compounds (VOC). The exposures were assessed during work operations on small-scale cooling installations like refrigerators and freezers. The repair workers' occupational exposures to refrigerants were moderate, and the major part of the exposures were associated with specific working procedures lasting for relatively short periods of time (<20 min). During these exposure events the concentrations were occasionally high (up to 42434 mg m(-3)). Although welding operations lasted only for short periods of time, HF was detected in 9 out of 15 samples when HCFC 22, HFC 134a or R404A had been used. Hydrogen chloride was detected in 3 out of 5 samples in air polluted with HCFC 22. Phosgene was not detected. A large number of VOCs in various concentrations were found during welding. Except for the applied refrigerants, halogenated compounds were only found in one sample.     

Development of a simple extraction cell with bi-directional continuous flow coupled on-line to ICP-MS for assessment of elemental associations in solid samples

A continuous-flow system comprising a novel, custom-built extraction module and hyphenated with inductively coupled plasma-mass spectrometric (ICP-MS) detection is proposed for assessing metal mobilities and geochemical associations in soil compartments as based on using the three step BCR (now the Measurements and Testing Programme of the European Commission) sequential extraction scheme. Employing a peristaltic pump as liquid driver, alternate directional flows of the extractants are used to overcome compression of the solid particles within the extraction unit to ensure a steady partitioning flow rate and thus to maintain constant operationally defined extraction conditions. The proposed flow set-up is proven to allow for trouble-free handling of soil samples up to 1 g and flow rates < or =10 mL min(-1). The miniaturized extraction system was coupled to ICP-MS through a flow injection interface in order to discretely introduce appropriate extract volumes to the detector at a given time and with a given dilution factor. The proposed hyphenated method demonstrates excellent performance for on-line monitoring of major and trace elements (Ca, Mn, Fe, Ni, Pb, Zn and Cd) released when applying the various extracting reagents as addressed in the BCR scheme, that is, 0.11 M CH(3)COOH, 0.1 NH(2)OH.HCl and 30% H(2)O(2), even when a well recognized matrix-sensitive detector, such as ICP-MS, is used. As a result of the enhanced temporal resolution of the ongoing extraction, insights into the breaking down of phases and into the kinetics of the metal release are obtained. With the simultaneous multielement detection capability of ICP-MS, the dynamic fractionation system presents itself as an efficient front-end for evaluation of actual elemental association by interelement comparison of metals leached concurrently during the extraction time. Thus, the intimate elemental association between Cd and Zn in contaminated soils could be assessed.     

Natural resource management in a protected area of the Indian Himalayas: a modeling approach for anthropogenic interactions on ecosystem

The concept of ecosystem conservation as a broad theme came into existence during the 1970s under the Man and Biosphere Programme (MAB) of the United Nations Educational, Scientific and Cultural Organization (UNESCO). The Indian Government followed this approach and chose the method to segregate the landscape for conservation of the ecosystem as well as for the development of the local economy and its people. We have examined the effect of this policy and concurrently developed a theoretical modeling approach to understand how human behavior is changing under shifting political, socioeconomic and environmental conditions. A specific focus has been on how the landscape is changing in the mountains of the Indian Himalayan region where about 10% of the total geographical area is converted into protected landscape for conservation of biodiversity. For local people living in the Himalayan mountains in India, agriculture is the main land use activity and is strongly linked to the forests in providing sustainability. There are several branches in the rural ecosystems where the local people's economy was centered. These include agriculture, animal husbandry, medicinal and aromatic plants cultivation, forest resource collection, tourism and other occupations. The greatest proportion of the population was engaged in the agriculture sector, whose contribution is high in the rural economy (61%); followed by animal husbandry (19%), forest resource collection for economic gain (18%), and medicinal and aromatic plants cultivation (1.5%). However, three decades ago the animal husbandry branch of the rural ecosystem was contributing the maximum share towards rural household income (40%) followed by tourism (35.2%), and lastly agriculture (14%). The desire of farmers to secure the optimum output from agricultural land use has resulted in an increase for resource collection from the forests. The people's perception (n = 1,648) regarding overall changes occurring in the region was varied and most showed that the current trend within rural ecosystems has emerged because of the implementation of conservation policies/creation of national park and biosphere reserve (80%), followed by limitation (22%), climate (20%), population growth (7%), national economy (10%) and least by socioeconomic change (5%). The theoretical agent model developed here draws attention to agent/farmer behavior and land resource use for his livelihood in the temporal dimension. The current study would be helpful to introduce new approaches for the development of the methodological and theoretical aspects associated with the complex human and ecosystem interactions in the Himalayan mountains for sustainable landscape development.     

Polychlorinated biphenyls (PCBs) in indoor air originating from sealants in contaminated and uncontaminated apartments within the same housing estate

Twenty-four congeners of polychlorinated biphenyls (PCBs) were measured in 83 air samples and 20 elastic sealants samples of apartments with PCB-containing sealants. In addition, PCBs were measured in 21 air samples from reference apartments located in an uncontaminated section of the same estate. The PCB_tot levels in the air of the contaminated section were 168-3843 ng m⁻³ (mean: 1030 ng m⁻³), while the mean levels in the reference apartments were 6.03 ng m⁻³. The sum of the 24 measured PCB congeners in sealants from the contaminated section was 187-221 680 mg kg⁻¹. Principal component analysis revealed four groups among the sealant samples with different congener compositions, only two of which were clearly similar to known PCB mixtures, while two were not. Significant correlations and intercorrelations were observed between the lower chlorinated congeners in air and sealant, e.g. for PCB 28_air and 28_seal (p = 0.04) and for PCB 28_air and 52_air, 52_seal. However, no correlation was observed between the lower chlorinated congeners and the sums of PCB (∑PCB₆ or ∑PCB₂₄) or the higher chlorinated congeners. Analysis of air concentrations in relation to questionnaire data indicated that the indoor air levels could be reduced by increased cleaning and airing frequencies.     

A dynamic modelling approach for estimating critical loads of nitrogen based on plant community changes under a changing climate

A dynamic model of forest ecosystems was used to investigate the effects of climate change, atmospheric deposition and harvest intensity on 48 forest sites in Sweden (n = 16) and Switzerland (n = 32). The model was used to investigate the feasibility of deriving critical loads for nitrogen (N) deposition based on changes in plant community composition. The simulations show that climate and atmospheric deposition have comparably important effects on N mobilization in the soil, as climate triggers the release of organically bound nitrogen stored in the soil during the elevated deposition period. Climate has the most important effect on plant community composition, underlining the fact that this cannot be ignored in future simulations of vegetation dynamics. Harvest intensity has comparatively little effect on the plant community in the long term, while it may be detrimental in the short term following cutting. This study shows: that critical loads of N deposition can be estimated using the plant community as an indicator; that future climatic changes must be taken into account; and that the definition of the reference deposition is critical for the outcome of this estimate.     

Monitoring of heavy metal concentrations in home outdoor air using moss bags

One monitoring station is insufficient to characterize the high spatial variation of traffic-related heavy metals within cities. We tested moss bags (Hylocomium splendens), deployed in a dense network, for the monitoring of metals in outdoor air and characterized metals’ long-term spatial distribution and its determinants in Girona, Spain. Mosses were exposed outside 23 homes for two months; NO₂ was monitored for comparison. Metals were not highly correlated with NO₂ and showed higher spatial variation than NO₂. Regression models explained 61-85% of Cu, Cr, Mo, Pb, Sb, Sn, and Zn and 72% of NO₂ variability. Metals were strongly associated with the number of bus lines in the nearest street. Heavy metals are an alternative traffic-marker to NO₂ given their toxicological relevance, stronger association with local traffic and higher spatial variability. Monitoring heavy metals with mosses is appealing, particularly for long-term exposure assessment, as mosses can remain on site many months without maintenance.     

BETR global--a geographically-explicit global-scale multimedia contaminant fate model

We present two new software implementations of the BETR Global multimedia contaminant fate model. The model uses steady-state or non-steady-state mass-balance calculations to describe the fate and transport of persistent organic pollutants using a desktop computer. The global environment is described using a database of long-term average monthly conditions on a 15° × 15° grid. We demonstrate BETR Global by modeling the global sources, transport, and removal of decamethylcyclopentasiloxane (D5).     

Environmental and health effects of nanomaterials in nanotextiles and façade coatings

Engineered nanomaterials (ENM) are expected to hold considerable potential for products that offer improved or novel functionalities. For example, nanotechnologies could open the way for the use of textile products outside their traditional fields of applications, for example, in the construction, medical, automobile, environmental and safety technology sectors. Consequently, nanotextiles could become ubiquitous in industrial and consumer products in future. Another ubiquitous field of application for ENM is fa?ade coatings. The environment and human health could be affected by unintended release of ENM from these products. The product life cycle and the product design determine the various environmental and health exposure situations. For example, ENM unintentionally released from geotextiles will probably end up in soils, whereas ENM unintentionally released from T-shirts may come into direct contact with humans and end up in wastewater. In this paper we have assessed the state of the art of ENM effects on the environment and human health on the basis of selected environmental and nanotoxicological studies and on our own environmental exposure modeling studies. Here, we focused on ENM that are already applied or may be applied in future to textile products and fa?ade coatings. These ENM's are mainly nanosilver (nano-Ag), nano titanium dioxide (nano-TiO(2)), nano silica (nano-SiO(2)), nano zinc oxide (nano-ZnO), nano alumina (nano-Al(2)O(3)), layered silica (e.g. montmorillonite, Al(2)[(OH)(2)/Si(4)O(10)]nH(2)O), carbon black, and carbon nanotubes (CNT). Knowing full well that innovators have to take decisions today, we have presented some criteria that should be useful in systematically analyzing and interpreting the state of the art on the effects of ENM. For the environment we established the following criteria: (1) the indication for hazardous effects, (2) dissolution in water increases/decreases toxic effects, (3) tendency for agglomeration or sedimentation, (4) fate during waste water treatment, and (5) stability during incineration. For human health the following criteria were defined: (1) acute toxicity, (2) chronic toxicity, (3) impairment of DNA, (4) crossing and damaging of tissue barriers, (5) brain damage and translocation and effects of ENM in the (6) skin, (7) gastrointestinal or (8) respiratory tract. Interestingly, some ENM might affect the environment less severely than they might affect human health, whereas the case for others is vice versa. This is especially true for CNT. The assessment of the environmental risks is highly dependent on the respective product life cycles and on the amounts of ENM produced globally.     

X-ray absorption and photoelectron spectroscopy investigation of selenite reduction by FeII-bearing minerals

The long-lived radionuclide 79Se is one of the elements of concern for the safe storage of high-level nuclear waste, since clay minerals in engineered barriers and natural aquifer sediments strongly adsorb cationic species, but to lesser extent anions like selenate (SeVIO4(2-)) and selenite (SeIVO3(2-)). Previous investigations have demonstrated, however, that SeIV and SeVI are reduced by surface-associated FeII, thereby forming insoluble Se0 and Fe selenides. Here we show that the mixed FeII/III (hydr)oxides green rust and magnetite, and the FeII sulfide mackinawite reduce selenite rapidly (< 1 day) to FeSe, while the slightly slower reduction by the FeII carbonate siderite produces elemental Se. In the case of mackinawite, both S(-II) and FeII surface atoms are oxidized at a ratio of one to four by producing a defective mackinawite surface. Comparison of these spectroscopic results with thermodynamic equilibrium modeling provides evidence that the nature of reduction end product in these FeII systems is controlled by the concentration of HSe(-); Se0 forms only at lower HSe(-) concentrations related to slower HSeO3(-) reduction kinetics. Even under thermodynamically unstable conditions, the initially formed Se solid phases may remain stable for longer periods since their low solubility prevents the dissolution required for a phase transformation into more stable solids. The reduction by Fe2+-montmorillonite is generally much slower and restricted to a pH range, where selenite is adsorbed (pH < 7), stressing the importance of a heterogeneous, surface-enhanced electron transfer reaction. Although the solids precipitated by the redox reaction are nanocrystalline, their solubility remains below 6.3 x 10(-8) M. No evidence for aqueous metal selenide colloids nor for Se sorption to colloidal phases was found. Since FeII phases like the ones investigated here should be ubiquitous in the near field of nuclear waste disposals as well as in the surrounding aquifers, mobility of the fission product 79Se may be much lower than previously assumed.