Uncertainties and novel prospects in the study of the soil carbon dynamics

Establishment of the Kyoto Protocol has resulted in an effort to look towards living biomass and soils for carbon sequestration. In order for carbon credits to be meaningful, sustained carbon sequestration for decades or longer is required. It has been speculated that improved land management could result in sequestration of a substantial amount of carbon in soils within several decades and therefore can be an important option in reducing atmospheric CO2 concentration. However, evaluation of soil carbon sources and sinks is difficult because the dynamics of soil carbon storage and release is complex and still not well understood. There has been rapid development of quantitative techniques over the past two decades for measuring the component fluxes of the global carbon cycle and for studying the soil carbon cycle. Most significant development in the soil carbon cycle study is the application of accelerator mass spectrometry (AMS) in radiocarbon measurements. This has made it possible to unravel rates of carbon cycling in soils, by studying natural levels of radiocarbon in soil organic matter and soil CO2. Despite the advances in the study of the soil carbon cycle in the recent decades, tremendous uncertainties exist in the sizes and turnover times of soil carbon pools. The uncertainties result from lack of standard methods and incomplete understanding of soil organic carbon dynamics, compounded by natural variability in soil carbon and carbon isotopic content even within the same ecosystem. Many fundamental questions concerning the dynamics of the soil carbon cycle have yet to be answered. This paper reviews and synthesizes the isotopic approaches to the study of the soil carbon cycle. We will focus on uncertainties and limitations associated with these approaches and point out areas where more research is needed to improve our understanding of this important component of the global carbon cycle.     

The fate and importance of organics in drinking water treatment: a review

In the pioneer days, the main driving forces for research of organics in drinking water treatment (DWT) were human health risks and optimisation of technology. The focus was on natural organic matter (NOM) structure, disinfection by-products (DBPs) formation, NOM removal by means of coagulation, adsorption, and oxidation, and development of the most efficient water treatment trains. Surprisingly, after decades of research, rapid development of analytical techniques and progress in risk assessment, the same driving forces are still in the limelight — although the topics have changed slightly. The attention switched from trihalomethanes to a new generation of DBPs. The definition of hydrophilic/hydrophobic NOM depends on the technique used for characterisation. It has become evident that numerous organic compounds can threaten water supply sources. Some of them had been ignored or overlooked in the past, but have recently been detected by advanced analytical tools even in drinking water. Prioritisation becomes priority per se. As far as processes are concerned, mainstream research has been following three lines: fouling mechanisms, application of hybrid processes and interactions between synthetic organic chemicals, other water constituents and materials used in DWT. Significant development has been made in membrane technology. This paper presents a broad overview of the recent organics research. Although the state-of-the-art technologies seem to have an answer to each and every question raised, it is still necessary to deal with specific problems on a case-by-case basis mainly due to the unique nature of NOM and different xenobiotics that may appear in various types of waters. In the end, human health risk, which derives from the presence/absence of organics, is only the tip of the iceberg — underneath lies a whole new universe — the socio-economic aspect of water treatment and quality that deserves much more attention.     

Current status and future needs for biological and environmental reference materials certified for methylmercury compounds.

A good quality control/quality assurance programme should be implemented in all environmental or health related studies on mercury and its organic compounds, particularly, for monomethylmercury (MeHg) which is the most toxic mercury compound. This can be achieved initially by analysing suitable certified reference materials (CRMs), which are available from various producers such as the National Institute of Standards and Technology (NIST) from USA, National Institute of Environmental Studies (NIES), National Research Council of Canada (NRCC), Standards, Measurements and Testing programme (SM&T) of the European Commission, and the International Atomic Energy Agency (IAEA). It is well understood that these materials are not covering present needs, as most of them are of the marine origin, while many laboratories are conducting research and monitoring in terrestrial ecosystems and fresh water environment. In addition, CRMs for human exposure assessment, such as blood, urine, and hair at several levels of concentrations are still lacking. Therefore, many other actions should be undertaken to achieve, improve and/or maintain quality of data, including participation in interlaboratory studies, proficiency testing and production of laboratory reference materials. A review of these actions has shown that MeHg compounds determination in samples such as soil, sediment and water is rather difficult and the results are also method dependent. In addition, it has been shown that some of the most frequently employed analytical methods may be a subject to spurious MeHg formation in the presence of high concentrations of inorganic mercury and organic matter. These findings have put a number of previous data on MeHg in question and consequently prompt actions were undertaken by a number of well experienced laboratories and producers of CRMs. So far, it is shown that the results obtained by various laboratories using different analytical techniques agree well with certified values in all RMs certified for MeHg. This suggests that comparability of data can be achieved, which however is not a guarantee of the true values.     

Assessment of human exposure to PCDDs,PCDFs and Co-PCBs using hair as a human pollution indicator sample I: Development of analytical method for human hair and evaluation for exposure assessment

Dioxins including polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and co-planar polychlorinated biphenyls (Co-PCBs) are highly toxic. Even at environmental pollution levels, they cause hormonal damage in women, and they have been shown to induce immunosuppression and genital function damage in humans. In this study, a new method using isotope dilution was established to detect PCDDs, PCDFs and Co-PCBs in human hair. This method, comprised of washing and cutting of hair, alkaline decomposition, hexane extraction, multilayer silica gel column chromatography, high performance liquid chromatography with a porous graphite carbon column and analysis by high resolution gas chromatography/high resolution mass spectrometry, enabled us to analyze PCDDs, PCDFs and Co-PCBs at trace levels of less than pg/g with good reproducibility. In addition, there was a correlation between some isomers in human hair and blood collected from identical donors. Human hair analysis is useful to evaluate human risk assessment including that due to environmental pollution.     

Probabilistic approaches in the effect assessment of toxic chemicals. What are the benefits and limitations?

There is an ongoing discussion whether in the environmental risk assessment for chemicals the so called 'deterministic' approach using point estimates of exposure and effect concentrations is still appropriate. Instead, the more detailed and scientifically sounder probabilistic methods that have been developed over the last years are widely recommended. Here, we present the results of a probabilistic effect assessment for the aquatic environment performed for the pesticide methyl parathion and compare them with the results obtained with the common deterministic approach as described in the EU Technical Guidance Document. Methyl parathion was chosen because a sufficient data set (acute toxicity data for about 70 species) was available. The assumptions underlying the probabilistic effect assessment are discussed in the light of the results obtained for methyl parathion. Two important assumptions made by many studies are: (i) a sufficient number of ecologically relevant toxicity data is available, (ii) the toxicity data follow a certain distribution such as log-normal. Considering the scarcity of data for many industrial chemicals, we conclude that these assumptions would not be fulfilled in many cases if the probabilistic assessment was applied to the majority of industrial chemicals. Therefore, despite the well-known limitations of the deterministic approach, it should not be replaced by probabilistic methods unless the assumptions of these methods are carefully checked in each individual case, which would significantly increase the effort for the assessment procedure.     

Occurrence of organic and inorganic biocides in the museum environment

In the museum environment organic and inorganic chemicals can be found, which originate from both outside and inside the building. Many of the contaminants may cause adverse effects on works of art and human health, but in the past, pollution research in museums has focused on the protection of artifacts, while the risk assessment for humans has been neglected. Especially, the application of biocides leads to a conflict of interest: on the one hand cultural assets have to be protected against microorganisms, insects and rodents while on the other hand it is essential to provide healthy conditions for museum staff and visitors. It has recently been shown that the release of organic indoor pollutants from building products is one of the main reasons for deterioration of artifacts. In this work, we present the results of screening measurements on biocides in different locations of German museums. The major components that could be identified were DDT, PCP, lindane, methoxychlor, naphthalene, chlorinated naphthalenes, 1,4-dichlorobenzene, PCBs and arsenic. It is demonstrated that the application of chlorinated organic compounds and arsenic for preventive conservation is one of the prime reasons for indoor pollution in museums and provides a potential for exposure. However, the concentrations in air, dust and material are widely different and a health risk for humans has to be evaluated case by case.     

A review of biomarker compounds as source indicators and tracers for air pollution

An overview of the application of organic geochemistry to the analysis of organic matter on aerosol particles is presented here. This organic matter is analyzed as solvent extractable bitumen/ lipids by gas chromatography-mass spectrometry. The organic geochemical approach assesses the origin, the environmental history and the nature of secondary products of organic matter by using the data derived from specific molecular analyses. Evaluations of production and fluxes, with cross-correlations can thus be made by the application of the same separation and analytical procedures to samples from point source emissions and the ambient atmosphere. This will be illustrated here with typical examples from the ambient atmosphere (aerosol particles) and from emissions of biomass burning (smoke). Organic matter in aerosols is derived from two major sources and is admixed depending on the geographic relief of the air shed. These sources are biogenic detritus (e.g., plant wax, microbes, etc.) and anthropogenic particle emissions (e.g., oils, soot, synthetics, etc.). Both biogenic detritus and some of the anthropogenic particle emissions contain organic materials which have unique and distinguishable compound distribution patterns (C₁₄-C₄₀). Microbial and vascular plant lipids are the dominant biogenic residues and petroleum hydrocarbons, with lesser amounts of the pyrogenic polynuclear aromatic hydrocarbons (PAH) and synthetics (e.g., chlorinated compounds), are the major anthropogenic residues. Biomass combustion is another important primary source of particles injected into the global atmosphere. It contributes many trace substances which are reactants in atmospheric chemistry and soot paniculate matter with adsorbed biomarker compounds, most of which are unknown chemical structures. The injection of natural product organic compounds into smoke occurs primarily by direct volatilization/steam stripping and by thermal alteration based on combustion temperature. Although the molecular composition of organic matter in smoke particles is highly variable, the molecular tracers are generally still source specific. Retene has been utilized as a tracer for conifer smoke in urban aerosols, but is not always detectable. Dehydroabietic acid is generally more concentrated in the atmosphere from the same emission sources. Degradation products from biopolymers (e.g., levoglucosan from cellulose) are also excellent tracers. An overview of the biomarker compositions of biomass smoke types is presented here. Defining additional tracers of thermally-altered and directly-emitted natural products in smoke aids the assessment of the organic matter type and input from biomass combustion to aerosols. The precursor to product approach of compound characterization by organic geochemistry can be applied successfully to provide tracers for studying the chemistry and dispersion of ambient aerosols and smoke plumes. Presented at the 6th FECS Conference on Chemistry and the Environment, Atmospheric Chemistry and Air Pollution, August 26–28, 1998, Copenhagen.     

Prospects and limitations of phytoremediation for the removal of persistent pesticides in the environment

The environmental problems that have arisen from the use of persistent pesticides in the past, and potential sources of further contamination have been discussed. The potential and limitations of phytoremediation for removal of pesticides in the environment have been reviewed. The enzymatic processes in plants that are known to be involved in phytodegradation of pesticides, and possibilities for enhancing them have also been discussed.     

Characterization of mucilage aggregates in Adriatic and Tyrrhenian Sea: structure similarities between mucilage samples and the insoluble fractions of marine humic substance

The appearance of gelatinous aggregates called mucilages causes serious damages to tourism and fishery industries of the Adriatic Sea. So, many studies have been planned and some of them are still in progress to clarify the origin and causes of the phenomenon. The scientific research has showed that mucilages are produced by several marine organisms when peculiar climatic and trophic conditions occur. Moreover, as far as the mucilage composition is concerned, although it is well known that polysaccharides give a high contribution, knowledge of the structural characteristics of mucilages and their relationship with the natural organic matter of the marine environment has not been clarified yet. In this paper a study on the characterization of the marine mucilage samples collected in the Adriatic and Tyrrhenian Seas is described. The study was performed by spectroscopic (infrared and colorimetric) techniques, and elemental analysis. The results showed that mucilage samples have chemical and structural similarities with the insoluble fraction of the marine humic substance (humin). According to experimental evidences it is possible to establish the relationship between mucilages and the dissolved organic matter (DOM) in the marine environment in order to identify the most likely pathways of mucilage formation.     

Utilising the Synergy between Plants and Rhizosphere Microorganisms to Enhance Breakdown of Organic Pollutants in the Environment (15 pp)

Background Phytoremediation is a promising technology for the cleanup of polluted environments. The technology has so far been used mainly to remove toxic heavy metals from contaminated soil, but there is a growing interest in broadening its applications to remove/degrade organic pollutants in the environment. Both plants and soil microorganisms have certain limitations with respect to their individual abilities to remove/breakdown organic compounds. A synergistic action by both rhizosphere microorganisms that leads to increased availability of hydrophobic compounds, and plants that leads to their removal and/or degradation, may overcome many of the limitations, and thus provide a useful basis for enhancing remediation of contaminated environments.Main Features The review of literature presented in this article provides an insight to the nature of plant-microbial interactions in the rhizosphere, with a focus on those processes that are relevant to the breakdown and/or removal of organic pollutants. Due consideration has been given to identify opportunities for utilising the plant-microbial synergy in the rhizosphere to enhance remediation of contaminated environments.Results and Discussion The literature review has highlighted the existence of a synergistic interaction between plants and microbial communities in the rhizosphere. This interaction benefits both microorganisms through provision of nutrients by root exudates, and plants through enhanced nutrient uptake and reduced toxicity of soil contaminants. The ability of the plant-microbial interaction to tackle some of the most recalcitrant organic chemicals is of particular interest with regard to enhancing and extending the scope of remediation technologies.Conclusions Plant-microbial interactions in the rhizosphere offer very useful means for remediating environments contaminated with recalcitrant organic compounds.Outlook A better knowledge of plant-microbial interactions will provide a basis for improving the efficacy of biological remediations. Further research is, however, needed to investigate different feedback mechanisms that select and regulate microbial activity in the rhizosphere.     

China’s wastewater discharge standards in urbanization

Background and purpose

China's environmental problems and pollution control have global implications. China??s water pollution has been increasing with its urbanization and industrialization. Although great efforts have been taken to keep its wastewater discharge standards in pace with the water pollution development and technological advances, many challenges remain. A summary of the past achievements and lessons as well as the current problems in water pollution may provide a basis for future improvements in China and a reference for other countries.

Methods

Statistical data are summarized to reveal the evolution of China??s population, wastewater discharge and corresponding discharge standards over the past four decades. In particular, the specific control indexes and number of controlled items are discussed in details. The present water pollution situation is clearly illustrated by the water pollution map and the water quality distribution diagram. A comparison between China??s present wastewater discharge standards and those in the USA and the EU are also presented to find the possibilities for future improvement.

Results

The historical origins, major challenges and future perspectives of China??s wastewater discharge standards are overviewed. The barriers and ongoing efforts for standards formulation and implementation are highlighted. Some suggestions for future endeavors are given.

Conclusions

China??s wastewater discharge standard system has seen significant improvement over the past decades, but it still has many defects and limitations. Nonetheless, unprecedented great efforts are underway to address all these challenges. More stringent standards and subsequently a cleaner water environment in China can be expected in the near future.     

Hair analysis: another approach for the assessment of human exposure to selected persistent organochlorine pollutants

Hair analysis was used for the assessment of exposure to organochlorine pollutants in specimens from Greece, Romania and Belgium. A simple method (using 3 N HCI as incubation reagent, liquid-liquid extraction with hexane/ dichloromethane (DCM), alumina/acid silica clean-up and GC-ECD/GC-MS analysis) was used for screening of specimens. The highest organochlorine load (up to 148 ng/g hair for the sum of PCB, DDT and hexachlorocyclohexane (HCH) isomers) was found in samples from a group of Greek women with past occupational exposure to pesticides. DDTs were the main organochlorine pollutants in Greek samples (up to 70%), while in Belgian hair samples their contribution was reduced to 40%. PCB mean concentration was higher in Belgian specimens (up to 14 ng/g hair). Lindane (y-HCH) was the main HCH isomer found in the samples (up to 82% in the Greek samples). Contribution of p,p'-DDT to the sum of DDTs was higher in Greek samples and indicates recent exposure to technical DDT. Similar PCB 153/sum PCBs ratios were found for each of the three countries suggesting similar sources of pollution with PCBs (mainly dietary). Artificially coloured hair samples were found to have lower, but not statistically significant concentrations of organochlorine pollutants than the non-coloured hair.     

Application of a random walk model to turbulent diffusion in complex terrain

A random walk model has been used for simulation of concentration patterns in complex terrain. For simplicity the problem has been treated only for line sources and two-dimensional topography. Results have been compared with wind-tunnel experiments, with a qualitatively good agreement. Although there are no difficulties from a technical point of view in applying random walk methods to complex terrain, some problems regarding the physical aspect of turbulent diffusion in inhomogenous flows still have to be considered more carefully.     

Modeling the formation of chlorination by-products in river waters with different quality

Water chlorination results in formation of a variety of organic compounds, known as chlorination by-products (CBPs), mainly trihalomethanes (THMs) and haloacetic acids (HAAs). Factors affecting their concentrations have been found to be organic matter content of water, pH, temperature, chlorine dose, contact time and bromide concentration, but the mechanisms of their formation are still under investigation. Within this scope, chlorination experiments have been conducted with river waters from Lesvos island, Greece, with different water quality regarding bromide concentration and organic matter content. The factors studied were pH, time and chlorine dose. The determination of CBPs was carried out by gas chromatography techniques. Statistical analysis of the results was focused on the development of multiple regression models for predicting the concentrations of total trihalomethanes and total HAAs based on the use of pH, reaction time and chlorine dose. The developed models, although providing satisfactory estimations of the concentrations of the CBPs, showed lower correlation coefficients than the multiple regression models developed for THMs only during previous study. It seems that the different water quality characteristics of the two river waters in the present study is responsible for this phenomenon. The results indicate that under these conditions the formation of THMs and HAAs in water has a more stochastic character, which is difficult to be described by the conventional regression techniques.     

Effects of airborne volatile organic compounds on plants

Routine measurements of volatile organic compounds (VOCs) in air have shown that average concentrations are very much smaller than those used in laboratory experiments designed to study the effects of VOCs on plants. However, maximum hourly concentrations of some VOCs can be 100 times larger than the average, even in rural air. Experimental studies have rarely extended for longer than a few days, so there is little information on potential long-term effects of exposure to small concentrations. This review considers the available evidence for long-term effects, based on laboratory and field data. Previous reviews of the literature from Germany and the USA are cited, prior to an assessment of the effects of individual VOCs. Although hydrocarbons from vehicle exhausts have been implicated in the observed effects on roadside vegetation, the evidence suggests that it is the nitrogen oxides in the exhaust gases that are mostly responsible. There is evidence that aromatic hydrocarbons can be metabolised in plants, although the fate of the metabolites is not known. There is a large literature on the effects of ethylene, because of its role as a plant hormone. Effects have been reported in the field, in response to industrial emissions, and dose-response experiments over several weeks in laboratory studies have clearly identified the potential for effects at ambient concentrations. The main responses are morphological (e.g. epinasty), which may be reversible, and on the development of flowers and fruit. Effects on seed production may be positive or negative, depending on the exposure concentration. Chlorinated hydrocarbons have been identified as potentially harmful to vegetation, but only one long-term experiment has studied dose-response relationships. As for ethylene, the most sensitive indication of effect was on seed production, although long-term accumulation of trichloroacetic acid in tissue may also be a problem. There is little evidence of the direct effects of oxygenated hydrocarbons on plants. Plants are a significant emission source of short-chain alcohols, aldehydes and ketones. Peroxyacetyl nitrate (PAN) has a well-documented history as damaging to vegetation. There have been few long-term experimental studies despite the field evidence for damaging effects. Early studies in California have been followed by more recent data from east Asia, but there is still a dearth of information on the potential for effects of PAN and related peroxyacyl nitrates on vegetation typical of regions around tropical and sub-tropical cities where PAN pollution is increasingly important. The lack of long-term measurements, coupled with the available evidence that effects are not linearly related to 'dose' measured as the product of exposure concentration and time, means that the possibility of adverse effects of VOCs on vegetation cannot be safely rejected, particularly in urban and industrial areas. Although reproductive processes (flowering, seed production) appear to be most sensitive, there have been no experimental studies on subsequent seed viability and the consequences at the ecosystem level of changes to plant phenology. The potential for VOC metabolites to accumulate in plant tissue has been demonstrated, but any subsequent effects on herbivores and phytophagous insects have yet to be investigated.     

Transport impacts on atmosphere and climate: Land transport

Emissions from land transport, and from road transport in particular, have significant impacts on the atmosphere and on climate change. This assessment gives an overview of past, present and future emissions from land transport, of their impacts on the atmospheric composition and air quality, on human health and climate change and on options for mitigation.In the past vehicle exhaust emission control has successfully reduced emissions of nitrogen oxides, carbon monoxide, volatile organic compounds and particulate matter. This contributed to improved air quality and reduced health impacts in industrialised countries. In developing countries however, pollutant emissions have been growing strongly, adversely affecting many populations. In addition, ozone and particulate matter change the radiative balance and hence contribute to global warming on shorter time scales. Latest knowledge on the magnitude of land transport's impact on global warming is reviewed here.In the future, road transport's emissions of these pollutants are expected to stagnate and then decrease globally. This will then help to improve the air quality notably in developing countries. On the contrary, emissions of carbon dioxide and of halocarbons from mobile air conditioners have been globally increasing and are further expected to grow. Consequently, road transport's impact on climate is gaining in importance. The expected efficiency improvements of vehicles and the introduction of biofuels will not be sufficient to offset the expected strong growth in both, passenger and freight transportation. Technical measures could offer a significant reduction potential, but strong interventions would be needed as markets do not initiate the necessary changes. Further reductions would need a resolute expansion of low-carbon fuels, a tripling of vehicle fuel efficiency and a stagnation in absolute transport volumes. Land transport will remain a key sector in climate change mitigation during the next decades.     

Increased Bioavailability of Mercury in the Lagoons of Lomé, Togo: The Possible Role of Dredging

Surface sediments of the lagoons of Lomé, Togo, were analyzed for mercury, methylmercury, and trace elements. Concentrations were greater than typical for natural lagoon sediments, and with greater variability within the Eastern lagoon compared to the Western one. The Eastern lagoon is larger and has been dredged in the past, while the Western lagoon, which also receives major waste inputs, has not been dredged and shows less tidal flushing. Accordingly, one naturally believes that the Eastern lagoon is cleaner and probably safe to use due to its natural resources, including fishes to eat. Unexpectedly, we describe here that mercury methylation was greater in the Eastern lagoon, indicating increased bioavailability of mercury, as probably facilitated by past dredging that decreased solid-phase retention of inorganic mercury. Urbanization has historically been more developed in the southern part of the lagoons, which is still reflected in contamination levels of sediment despite dredging, probably because sources of contamination are still more important there today. Such urban contamination emphasizes the need to regulate waste discharges and possible airborne contamination in growing cities of developing countries, and implements environmental and public health monitoring, especially in relation to misbelieves systematically associated with the cleansing effect of dredging activity.     

HCH contamination from former pesticide production in Brazil—a challenge for the Stockholm Convention implementation

Hexachlorocyclohexane (HCH) isomers (α-, β- and γ- HCH [lindane]) were recently added to the list of persistent organic pollutants regulated by the Stockholm Convention, and therefore, the legacy of HCH and lindane production has become an issue of global relevance. The production of lindane with the much larger quantities of associated waste isomers has generated large waste deposits and contaminated sites. This article presents an overview of HCH-polluted sites in Brazil as a basis for further activities related to the Stockholm Convention. The locations of HCH stockpiles and contaminated sites in Brazil arising from production and formulation have been compiled and mapped. This shows that the measures taken over the past 25 years have not resulted in remediation of the HCH pollution. An exposure risk study has been summarised for one major site and is included to demonstrate the contemporary relevance of the contamination. Major site remediation efforts are planned at one site but people live close to several other sites, and there is an urgent need of further assessments and remediation to ensure the protection of human health and the environment. The Stockholm Convention requires a systematic approach and should be adopted for the assessment of all sites and appropriate isolation/remediation measures should be facilitated. The appropriate planning of these activities for the production site in Rio de Janeiro could be a positive contribution for Rio+20 highlighting that green economy and sustainable production also include the appropriate management of legacies of historic production of an industrial sector (here the organochlorine industry).