The U.S. Experience in Promoting Sustainable Chemistry (9 pp)

- Sustainable chemistry - Section editors: Klaus Günter Steinhäuser, Steffi Richter, Petra Greiner, Jutta Penning, Michael AngrickBackground, Aim and Scope Recent developments in European chemicals policy, including the Registration, Evaluation and Authorization of Chemicals (REACH) proposal, provide a unique opportunity to examine the U.S. experience in promoting sustainable chemistry as well as the strengths and weaknesses of existing policies. Indeed, the problems of industrial chemicals and limitations in current regulatory approaches to address chemical risks are strikingly similar on both sides of the Atlantic. We provide an overview of the U.S. regulatory system for chemicals management and its relationship to efforts promoting sustainable chemistry. We examine federal and state and examine lessons learned from this system that can be applied to developing more integrated, sustainable approaches to chemicals management.Main Features There is truly no one U.S. chemicals policy, but rather a series of different un-integrated policies at the federal, regional, state and local levels. While centerpiece U.S. Chemicals Policy, the Toxic Substances Control Act of 1976, has resulted in the development of a comprehensive, efficient rapid screening process for new chemicals, agency action to manage existing chemicals has been very limited. The agency, however, has engaged in a number of successful, though highly underfunded, voluntary data collection, pollution prevention, and sustainable design programs that have been important motivators for sustainable chemistry. Policy innovation in the establishment of numerous state level initiatives on persistent and bioaccumulative toxics, chemical restrictions and toxics use reduction have resulted in pressure on the federal government to augment its efforts.Results and Conclusions It is clear that data collection on chemical risks and phase-outs of the most egregious chemicals alone will not achieve the goals of sustainable chemistry. These alone will also not internalize the cultural and institutional changes needed to ensure that design and implementation of safer chemicals, processes, and products are the focus of the future. Thus, a more holistic approach of ‘carrots and sticks’ – that involves not just chemical producers but those who use and purchase chemicals is necessary. Some important lessons of the US experience in chemicals management include: (1) the need for good information on chemicals flows, toxic risks, and safer substances.; (2) the need for comprehensive planning processes for chemical substitution and reduction to avoid risk trade-offs and ensure product quality; (3) the need for technical and research support to firms for innovation in safer chemistry; and (4) the need for rapid screening processes and tools for comparison of alternative chemicals, materials, and products.     

The Case of Sarno River (Southern Italy). Effects of geomorphology on the environmental impacts (8 pp)

Background, Aim and Scope Analysis of the morphological, geological and environmental characteristics of the Sarno River basin has shown the present degraded condition of the area. Over the past thirty years, the supply of untreated effluent of domestic, agricultural and industrial origin has ensured the presence of high concentrations of pollutants, including heavy metals. The geological context of the catchment area has played a major part in determining the current ecological conditions and public health problems: while human activity has modified the landscape, the natural order has indirectly contributed to increasing the environmental impact. Results and Discussion The health situation is precarious as the basin's inhabitants feed on agricultural and animal products, and use polluted water directly or indirectly. The hazard of contracting degenerative illnesses of the digestive or respiratory apparatus, bacterial infections or some neoplasia has gradually increased, especially in the last five years. Moreover, polluted basin waters flowing into the Bay of Naples increase sea water contamination, thereby damaging tourism, public health and degrading the local littoral quality. Conclusion The overview presented shows how the environmental state of the Sarno River basin gives considerable cause for concern. The basin's complex geomorphologic setting has a direct bearing on local environmental and health conditions. The analysis of the available data demonstrates how the physical aspects of the area are closely linked to the diffusion and concentration of the pollutants, and how the latter ones have a large influence on the hygienic-sanitary conditions of the local population. Recommendation and Perspective Specific interventions need to be undertaken to monitor and improve the chemical, physical and microbiological conditions of water and sediments, especially in light of the geomorphological vulnerability of the river basin.     

Fragrances in the Environment: Pleasant odours for nature? (9 pp)

Goal, Scope and Background Fragrance preparations or perfumes are used in an increasing variety of applications, as for example washing, cleansing, personal care products, consumer goods or in applications to modify indoor air. However, up to now, little is known to the general or scientific public about their chemical identity and the use pattern of single substances, not even for high production volume chemicals. Some toxicological data are published for a comparatively small number of substances with a focus on sensitisation and dermal effects, while other effects are neglected. Information on ecotoxicity and environmental fate are rare, especially for long-term exposure. Data for a detailed hazard and risk analysis are available in exceptional cases only. According to the current legal situation, fragrance industry is self-regulated, which means that pre-market risk evaluation is not required for most fragrances. Odour and the ability to smell play a major role for wildlife for all taxonomic groups. Reproductive and social behaviour, defence, communication and orientation depend on volatile compounds which can be identical to those used in fragrance preparations. Our interdisciplinary approach leads to the question of whether and, if so, to what extent anthropogenic fragrances may influence life and reproduction of organisms in the environment. Main Features Information from literature on use, exposure and biological effects was combined to analyse the state of knowledge. Following an overview of the amounts of fragrances used in different consumer products and their release into the environment, the roles of odours in nature are shown for a selection of compounds. Existing regulation was analysed to describe the data basis for environmental risk evaluation. Finally, recommendations for further action are derived from these findings. Results Three main results were elaborated: First, fragrance substances are continuously discharged in large amounts into the environment, especially via the waste water. Second, there are some indications of negative effects on human health or the environment, although the data basis is very thin due to the self regulation of the fragrance industry and the regulatory situation of fragrance substances. Third, many odoriferous substances used by man are identical to those which are signal substances of environmental organisms at very low concentrations, thus giving rise to specific mode of actions in the ecosystem. Recommendations For the adequate risk assessments of fragrances, test results on their unspecific as well as their specific effects as signal substances are needed. This would imply prioritisation methods and development of useful test methods for specific endpoints for appropriate risk assessments. Before a comprehensive testing and evaluation of results has been finished, a minimization of exposure should be envisaged. Eco-labelling of products containing acceptable fragrance ingredients could be a first step and provide consumers with the respective information. Transparency concerning the fragrance ingredients used and their biological potency will help to build up confidence between producers and consumers. Conclusions and Perspectives The interdisciplinary approach, bringing together chemical, biological, toxicological and ecotoxicological data with information provided by manufacturers and with legal and consumer aspects, offers new insights into the field of fragrance substances used in consumer products. The amounts and application fields of fragrance substances increases while fate and effects in the environment are hardly known. The current legal situation is not suited to elucidate the effects of fragrances on human health and the environment sufficiently, especially as it was shown that fragrances may play a considerable role in the ecosystem on the behaviour of organisms. According to the precautionary principle, the lack of knowledge should best be tackled by reducing exposure, especially for compounds such as fragrance substances where no ethical reasons object a substitution by less hazardous chemicals. ESS-Submission Editor: Dr. Thomas Knacker (th-knacker@ect.de)     

Indicators for Chemicals: Sources,impacts and policy performance (5 pp)

Background Different types of indicators have been developed to describe the impact of chemicals on society and environment. Due to the high number of substances and their different types of use, most of these indicators are directed to specific areas of interest – regarding workplace safety, environmental health or consumer health. They address a specific subset of chemicals and can be used for monitoring enterprise-specific, national or international management measures. Main Features A survey of existing indicators for chemicals has shown that indicators already exist for a remarkable number of problem fields. As soon as the release and the environmental fate of chemicals are taken into account, the complexity of the approaches increases considerably. The distinction between indicators for drivers, pressures, state, impacts and responses, as proposed by the European Environmental Agency, supports the identification of proper indicators for a specific type of problem. Discussion and Conclusions. No single indicator exists which is able to cover the whole range of chemicals and their applications. Several indicator approaches cover at least a subset of the most relevant substances. If they are intended to be used for European monitoring, robust data must be provided by EU Member States. Chemicals in enterprises (ancillary inputs as well as process chemicals) are an important element of in-plant material flow management – in terms of occupational safety and health as well as environmental protection. Existing indicators for hazardous chemicals can be a valuable tool for process and product refinement regarding hazardous chemicals, especially for enterprises. Outlook Indicators for production and impact of chemicals, as well as policy performance indicators, are essential elements in order to monitor the management of chemicals. They have to be established for the national and for the EU level.     

Survey of dioxin sources in the Baltic Region (extended summary)

The present paper summarises the results of the project: 'Survey of Anthropogenic Sources of Dioxins and Furans in the Baltic Region'. As a part of the project, inventories have been carried out in Estonia, Latvia, Lithuania and Poland by applying the toolkit for quantification of dioxin and furan releases developed by UNEP Chemicals. The main route of direct releases to the environment is emission to air. Total emission to air from Poland was estimated at 490 (88-1,300) g I-TEQ/year, whereas the emissions from Estonia, Latvia and Lithuania were estimated as being 14 (2.4-54), 23 (2.6-63) and 17 (2.6-38) g I-TEQ, respectively. In general, the uncertainty on the estimates is very high, and recommendations regarding further development of the inventories have been made, and measures for reducing the releases have been provided.     

Seasonal variation of organochlorine contaminants in bonito (Sarda sarda L. 1758) and anchovy (Engraulis encrasicolus L. 1758) in Black Sea region, Turkey

The concentrations of indicator polychlorinated biphenyls (PCBs) and organochlorine insecticides were determined in bonito (Sardasarda L. 1758) and anchovy (Engraulisencrasicolus L. 1758) from the Black Sea, Turkey. Concentrations of total indicator PCBs ranged between <1-17.0 in bonito, and <1-17.5 ng/g fresh weight in anchovy, and total of 1,1,1-trichloro-2,2-bis-chlorophenyl-ethane and its metabolites’ (DDTs) concentrations ranged between 13.4-26.3, and 2.96-19.0 ng/g fresh weight in bonito and anchovy respectively. PCB 52, p,p′-DDE and endosulfan (α + β) were found dominant in both of the fish species. Except endosulfan, and some DDT metabolites, none of the studied organochlorine pesticides was detected in the fish samples. Concentrations of PCBs in anchovy were found higher than those in bonito, whereas DDT and endosulfan concentrations were found similar in both of the fish species. All of the fish samples had residue concentrations below the maximum residue limits (MRL) recommended by FAO/WHO Codex Alimentarius Commission.     

The role of DDE,PCB, coplanar PCB and eggshell parameters for reproduction in the white-tailed sea eagle (Haliaeetus albicilla) in Sweden

The reproduction of white-tailed sea eagles was monitored in 1964-1999 in 3 differently contaminated sub-populations: Baltic Sea coast (Bp), inland central Sweden (Ip) and Lapland (Lp). 249 dead eggs from 205 clutches were obtained for analyses of DDE and PCBs and for eggshell measurements. A desiccation index (Di) value was calculated for each egg as a measure of water loss through the shell. In the highly contaminated Bp, p,p'-DDE concentrations in the eggs decreased continuously and 5-fold during the study period and PCB concentrations decreased 3-fold from the mid 1980s. The PCB pattern changed slightly over time towards more high-chlorinated congeners but the relative toxicity of the PCB mixture, expressed as 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQ), remained constant and TEQ can be assumed to have decreased in a similar way as PCB over time. Productivity (P), shell thickness (St), shell index (Si) and Di increased over time in the Bp but no change in Di or productivity occurred in the Lp, where residue concentrations were 5-8 times lower. P of the Bp was not correlated to St or Si but was negatively correlated to Di, DDE and PCB. An S-shaped dose-response relationship was indicated between P and DDE. After 1988, when the PCB/DDE ratio was considerably higher than previously, PCB but not DDE concentrations were significantly higher in eggs with dead embryos as compared to undeveloped eggs, implying lethal concentrations of PCB, and a LOEL of 320 pg g-1 TEQ is suggested for embryo mortality. In a subset of 21 eggs, representing productive and unproductive females, analyzed for a selection of coplanar PCB congeners, tris(4-chlorophenyl) methanol and bis(4-chlorophenyl) sulphone, there was no evidence for a correlation between P and any of these compounds. A reduction in residue concentrations in old females did not lead to increased P or improved Di-values, indicating a remaining effect from a previous, higher exposure to contaminants. The inability to reproduce included a high rate of undeveloped eggs, indicating effects at a prezygotic stage. P showed the strongest correlation with Di, and Di was most strongly correlated to DDE. Thus, the remaining effect of previous exposure resulted in a stronger correlation to the symptom (Di) rather than to the suggested causative agent (DDE). LOEL values for depressed P were estimated at 120 micrograms g-1 DDE and 500 micrograms g-1 PCB (lipid basis). It is concluded that the major reason for depressed P during the study period was DDE, but that effects also from PCB were largely concealed by the effects from DDE.     

The role of the cadmium-binding protein response of the digestive gland of the Yesso scallop Mizuhopecten yessoensis (Jay, 1857) for marine environmental assessments

Environmental Science and Pollution Research - The ability of Pectinidae to accumulate heavy metals and store them in their tissues allows the use of scallops for biomonitoring marine pollution....     

The intestinal parasite Pomphorhynchus laevis (Acanthocephala) from barbel as a bioindicator for metal pollution in the Danube River near Budapest, Hungary

Concentrations of As, Al, Ag, Ba, Bi, Cd, Co, Cr, Cu, Fe, Ga, Mg, Mn, Ni, Pb, Sb, Sn, Sr, Tl, V and Zn were analyzed by inductively coupled mass spectrometry (ICP-MS) in the intestinal helminth Pomphorhynchus laevis and its host Barbus barbus. The fish were caught in the Danube river downstream of the city of Budapest (Hungary). Ten out of twenty one elements analyzed were found at higher concentrations in the acanthocephalan than in different tissues (muscle, intestine, liver and kidney) of barbel. Considering the fish tissues, most of the elements were present at highest concentrations in liver, followed by kidney, intestine and muscle. Spearman correlation analyses indicate that there is competition for metals between the parasites and the host. The negative relationships between parasite number and metal levels in organs of the barbel support this hypothesis. The bioconcentration factors for Ag, As, Ba, Bi, Cu, Ga, Mn, Pb, Sr, Tl, and Zn showed that the parasites concentrated metals to a higher degree than the fish tissues. They accumulated the metals As, Cd, Cu, Fe, Ni, Pb, Sr and Zn even better than established bioindicators such as the mussel Dreissena polymorpha as revealed by data from the literature. The results presented here emphasize that acanthocephalans of fish are very useful as sentinels for metal pollution in aquatic ecosystems. Ratio of metal concentrations in the parasites and the host tissues provide additional information. Not including acanthocephalans in accumulation bioindication studies with fishes (as still customarily done) may lead to false results.     

Surface Consolidation of Pentelic Marble: Criteria for the selection of methods and materials - The Acropolis case (6 pp)

Goal and Scope In order to realize surface consolidation of Pentelic marble on the Acropolis monuments, we have collected the criteria that have to be fulfilled by the methods and materials without side effects on the marbles (and other stones). When the existing methods and materials did not satisfy the requirements (criteria), we invented new ones.Methods The criteria were collected from the literature, by thermodynamic and kinetic viewpoints, by laboratory experiments and in situ observations on monuments, both in Greece and in several countries in which the various methods and materials were applied. Concerning our method of ‘Inversion of sulfation’, performed by spraying a K2CO3 solution, its concentration and its temperature were controlled in order to have a total inversion (certified by liquid crystals) of gypsum back to CaCO3. For the new material of ours, ‘Reinforced Lime’, in order to eliminate the disadvantages of plain lime (low carbonation rate, low mechanical properties of CaCO3 formed, lack of carbonation in the bulk of lime), measurements of the rate of carbonation were performed in plain lime and in lime with a different CaCO3 concentration beforehand as well as in a different CO2 environments, using DTG and XRD to measure the rate of carbonation. The detachment (kg/cm2) of marble specimens stuck by lime in each case was also measured. A microscope was also used to measure the dimensions of the grain in each case as well as ammonium citrate and thymolphthalein to certify the depth of carbonation in each case. Part of the work was communicated in an international congress.Results A table with the criteria of the selection of the methods and materials for the consolidation of Pentelic marble surfaces (and other stones) was established. None of the employed methods and materials fulfilled the criteria. Only the ‘Inversion of gypsum ‘ and the ‘Reinforced Lime’ were adopted and applied to the Acropolis monuments and to other monuments in Greece and in several other countries.Recommendation and Outlook All criteria must be used for the selection of methods and materials for the consolidation of the monument surfaces. This is why we have already studied with the same procedures, methods and materials for restoration, surface cleaning and protection.     

Comparison of Microwave Assisted Extraction with Conventional (Homogenization,Vortexing) for the Determination of Incurred Salinomycin in Chicken Eggs and Tissues

Abstract

Incurred and fortified salinomycin residues were extracted from chicken tissues and eggs by homogenization, vortexing and by microwave assisted extraction. The salinomycin residues were quantitated by liquid chromatography following postcolumn derivatization with either vanillin or 4-dimethylamino-benzaldehyde and detected at 520 or 592 nm, respectively. Comparison of residue data indicated that microwave assisted extraction performed as well as the vortexing technique in extracting salinomycin residues in the tissues of laying chickens that were fed meal containing drugs at various level. In the present study, extracts from homogenizing could not be analyzed directly without clean up. Therefore, microwave assisted extraction appears to be a reliable, reproducible, and economical substitute for routinely used homogenization and vortexing extraction techniques.     

Environmental prospection for PCDD/PCDF, PAH, PCB and heavy metals around the incinerator power plant of Reggio Emilia town (Northern Italy) and surrounding main roads

Samples of soil, sediment and pine needles from the Reggio Emilia area were analysed in order to estimate the environmental pollution caused by an MSWI. PCDD/PCDF, PCB, PAH and metals were analysed in the collected samples. The data obtained showed relatively low pollution levels. Indeed, the PCDD/PCDF and PCB data were comparable to the values usually found in the grazing areas of the European Union countries. Metal concentrations in soils and sediments may be related to local geological occurrences and to agricultural activities. PAH values are significantly lower than the limit values set by the Italian law.     

Ecotoxicological Assessment of Sediment, Suspended Matter and Water Samples in the Upper Danube River. A pilot study in search for the causes for the decline of fish catches (12 pp)

Goals, Scope and Background Fish populations, especially those of the grayling (Thymallus thymallus), have declined over the last two decades in the upper Danube River between Sigmaringen and Ulm, despite intensive and continuous stocking and improvement of water quality since the 1970s. Similar problems have been reported for other rivers, e.g. in Switzerland, Great Britain, the United States and Canada. In order to assess if ecotoxicological effects might be related to the decline in fish catch at the upper Danube River, sediment, suspended matter and waste water samples from sewage treatment plants were collected at selected locations and analyzed in a bioanalytical approach using a battery of bioassays. The results of this pilot study will be used to decide if a comprehensive weight-of-evidence study is needed. Methods Freeze-dried sediments and suspended particulate matters were extracted with acetone in a Soxhlet apparatus. Organic pollutants from sewage water were concentrated using XAD-resins. In order to investigate the ecotoxicological burden, the following bioassays were used: (1) neutral red assay with RTL-W1 cells (cytotoxicity), (2) comet assay with RTLW1 cells (genotoxicity), (3) Arthrobacter globiformis dehydrogenase assay (toxicity to bacteria), (4) yeast estrogen screen assay (endocrine disruption), (5) fish egg assay with the zebrafish (Danio rerio; embryo toxicity) and (6) Ames test with TA98 (mutagenicity). Results and Discussion The results of the in vitro tests elucidated a considerable genotoxic, cytotoxic, mutagenic, bacteriotoxic, embryotoxic and estrogenic burden in the upper Danube River, although with a very inhomogeneous distribution of effects. The samples taken from Riedlingen, for example, induced low embryo toxicity, but the second highest 17β-estradiol equivalent concentration (1.8 ng/L). Using the fish egg assay with native sediments, a broad range of embryotoxic effects could be elucidated, with clear-cut dose-response relationships for the embryotoxic effects of contaminated sediments. With native sediments, embryotoxicity was clearly higher than with corresponding pore waters, thus corroborating the view that – at least for fish eggs – the bioavailability of particle-bound lipophilic substances in native sediments is higher than generally assumed. The effect observed most frequently in the fish egg assay was a developmental delay. A comparison of our own results with locations along the rivers Rhine and Neckar demonstrated similar or even higher ranges of ecotoxicological burdens in the Danube River. Conclusions The complex pattern of ecotoxicological effects caused by environmental samples from the Danube River, when assessed in an in vitro biotest battery using both acute and more specific endpoints, showed that integration of different endpoints is essential for appropriate hazard assessment. Overall, the ecotoxicological hazard potential shown has indeed to be considered as one potential reason for the decline in fish catches at the upper Danube River. However, based on the results of this pilot study, it is not possible to elucidate that chemically induced alterations are responsible for the fish decline. Recommendations and Perspective . In order to confirm the ecological relevance of the in vitro results for the situation in the field and especially for the decline of the grayling and other fishes, further integrated investigations are required. For linking the weight of evidence obtained by in vitro assays and fish population investigations, the application of additional, more specific biomarkers (e.g. vitellogenin induction, EROD and micronucleus assay) has been initiated in fish taken from the field as well as in situ investigations.