25 years monitoring of PAHs and petroleum hydrocarbons biodegradation in soil.

Biodegradation of polycyclic aromatic hydrocarbons (PAHs) and total petroleum hydrocarbons (TPH) in sediment and soil has been monitored on seven experimental fields during periods up to 25 years. With this unique dataset, we investigated long-term very slow biodegradation under field conditions. . The data show that three biodegradation rates can be distinguished for PAHs: 1) rapid degradation during the first year, 2) slow degradation during the following 6 years and 3), subject of this paper, a very slow degradation after 7 years until at least 25 years. Beside 2-, 3- and 4-ring PAHs, also 5- and 6-ring PAHs (aromatic rings) were degraded, all at the same rate during very slow degradation. In the period of very slow degradation, 6% yr-1 of the PAHs present were removed in five fields and 2% yr-1 in two other fields, while in the same period no very slow degradation of TPH could be observed. The remaining petroleum hydrocarbons were high boiling and non-toxic. Using the calculated degradation rates and the independently measured bioavailability of the PAHs (Tenax-method), the PAHs degradation curves of all seven monitored fields could be modelled. Applying the model and data obtained with the Tenax-method for fresh contaminated material, results of long-term biodegradation can be predicted, which can support the use of bioremediation in order to obtain a legally acceptable residual concentration.

Emerging pollutants in the EU: 10 years of NORMAN in support of environmental policies and regulations.

In 2005, the European Commission funded the NORMAN project to promote a permanent network of reference laboratories and research centers, including academia, industry, standardization bodies, and NGOs. Since then, NORMAN has (i) facilitated a more rapid and wide-scope exchange of data on the occurrence and effects of contaminants of emerging concern (CECs), (ii) improved data quality and comparability via validation and harmonization of common sampling and measurement methods (chemical and biological), (iii) provided more transparent information and monitoring data on CECs, and (iv) established an independent and competent forum for the technical/scientific debate on issues related to emerging substances. NORMAN plays a significant role as an independent organization at the interface between science and policy, with the advantage of speaking to the European Commission and other public institutions with the "bigger voice" of more than 70 members from 20 countries. This article provides a summary of the first 10 years of the NORMAN network. It takes stock of the work done so far and outlines NORMAN's vision for a Europe-wide collaboration on CECs and sustainable links from research to policy-making. It contains an overview of the state of play in prioritizing and monitoring emerging substances with reference to several innovative technologies and monitoring approaches. It provides the point of view of the NORMAN network on a burning issue-the regulation of CECs-and presents the positions of various stakeholders in the field (DG ENV, EEA, ECHA, and national agencies) who participated in the NORMAN workshop in October 2016. The main messages and conclusions from the round table discussions are briefly presented.

A Collaborative Evaluation of LC-MS/MS Based Methods for BMAA Analysis: Soluble Bound BMAA Found to Be an Important Fraction.

Exposure to ß-N-methylamino-l-alanine (BMAA) might be linked to the incidence of amyotrophic lateral sclerosis, Alzheimer's disease and Parkinson's disease. Analytical chemistry plays a crucial role in determining human BMAA exposure and the associated health risk, but the performance of various analytical methods currently employed is rarely compared. A CYANOCOST initiated workshop was organized aimed at training scientists in BMAA analysis, creating mutual understanding and paving the way towards interlaboratory comparison exercises. During this workshop, we tested different methods (extraction followed by derivatization and liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) analysis, or directly followed by LC-MS/MS analysis) for trueness and intermediate precision. We adapted three workup methods for the underivatized analysis of animal, brain and cyanobacterial samples. Based on recovery of the internal standard D3BMAA, the underivatized methods were accurate (mean recovery 80%) and precise (mean relative standard deviation 10%), except for the cyanobacterium Leptolyngbya. However, total BMAA concentrations in the positive controls (cycad seeds) showed higher variation (relative standard deviation 21%-32%), implying that D3BMAA was not a good indicator for the release of BMAA from bound forms. Significant losses occurred during workup for the derivatized method, resulting in low recovery (<10%). Most BMAA was found in a trichloroacetic acid soluble, bound form and we recommend including this fraction during analysis.

From Bioavailability Science to Regulation of Organic Chemicals.

The bioavailability of organic chemicals in soil and sediment is an important area of scientific investigation for environmental scientists, although this area of study remains only partially recognized by regulators and industries working in the environmental sector. Regulators have recently started to consider bioavailability within retrospective risk assessment frameworks for organic chemicals; by doing so, realistic decision-making with regard to polluted environments can be achieved, rather than relying on the traditional approach of using total-extractable concentrations. However, implementation remains difficult because scientific developments on bioavailability are not always translated into ready-to-use approaches for regulators. Similarly, bioavailability remains largely unexplored within prospective regulatory frameworks that address the approval and regulation of organic chemicals. This article discusses bioavailability concepts and methods, as well as possible pathways for the implementation of bioavailability into risk assessment and regulation; in addition, this article offers a simple, pragmatic and justifiable approach for use within retrospective and prospective risk assessment.

Positioning activated carbon amendment technologies in a novel framework for sediment management.

Contaminated sediments can pose serious threats to human health and the environment by acting as a source of toxic chemicals. The amendment of contaminated sediments with strong sorbents like activated C (AC) is a rapidly developing strategy to manage contaminated sediments. To date, a great deal of attention has been paid to the technical and ecological features and implications of sediment remediation with AC, although science in this field still is rapidly evolving. This article aims to provide an update on the recent literature on these features, and provides a comparison of sediment remediation with AC to other sediment management options, emphasizing their full-scale application. First, a qualitative overview of advantages of current alternatives to remediate contaminated sediments is presented. Subsequently, AC treatment technology is critically reviewed, including current understanding of the effectiveness and ecological safety for the use of AC in natural systems. Finally, this information is used to provide a novel framework for supporting decisions concerning sediment remediation and beneficial reuse.

Towards bioavailability-based soil criteria: past, present and future perspectives.

Bioavailability has been used as a key indicator in chemical risk assessment yet poorly quantified risk factor. Worldwide, the framework used to assess potentially contaminated sites is similar, and the decisions are based on threshold contaminant concentration. The uncertainty in the definition and measurement of bioavailability had limited its application to environment risk assessment and remediation. Last ten years have seen major developments in bioavailability research and acceptance. The use of bioavailability in the decision making process as one of the key variables has led to a gradual shift towards a more sophisticated risk-based approach. Now a days, many decision makers and regulatory organisations 'more readily accept' this concept. Bioavailability should be the underlying basis for risk assessment and setting remediation goals of those contaminated sites that pose risk to environmental and human health. This paper summarises the potential application of contaminant bioavailability and bioaccessibility to the assessment of sites affected by different contaminants, and the potential for this to be the underlying basis for sustainable risk assessment and remediation in Europe, North America and Australia over the coming decade.

Incorporating availability/bioavailability in risk assessment and decision making of polluted sites, using Germany as an example.

Nearly all publications dealing with availability or bioavailability of soil pollutants start with the following statement: the determination of total pollutant content will lead to an over-estimation of risk. However, an assessment of contaminated sites should be based on the determination of mobile fractions of pollutants, and the fractions with potential for mobilisation that threaten groundwater and surface water, and the actual and potential fractions available for uptake by plants, soil microflora and soil organisms. After reviewing the literature for method proposals concerning the determination of available/bioavailable fractions of contaminants with respect to leaching, plants, microorganisms (biodegradation) and soil organisms, we propose a testing and assessment scheme for contaminated sites. The proposal includes (i) already accepted and used methods, (ii) methods which are under standardisation, and (iii) methods for which development has just started in order to promote urgently needed research.

Bioavailability as a tool in site management.

Bioavailability can form the basis for describing potential risks that contaminants pose to the environment and human health, and for determining remedial options to reduce risks of contaminant dispersal and toxicity. In assessments of polluted sites, methods to measure bioavailability can lead to a realistic appraisal of the potential risks from exposure to contaminants. For remediation purposes the application of the principles of bioavailability can result in practices that reduce bioavailability and consequently the risk of contaminants. Moreover the costs of remediation can be reduced. Examples from projects with organic contaminants (PAHs, pesticides and PFOS) and heavy metals in The Netherlands, Mali, Mauretania, Australia and Taiwan are presented. It is shown that using bioavailability principles in risk-based approaches is an attractive option in terms of both cost and in situ management of contaminated sites. Regulatory and public acceptance is, however, still the Achilles heel of these new remediation strategies.

Estimation of in situ sediment-to-water fluxes of polycyclic aromatic hydrocarbons, polychlorobiphenyls and polybrominated diphenylethers.

Sediment-water fluxes of hydrophobic organic chemicals (HOC) may affect the quality of surface waters. Here, we present an approach to derive such fluxes from (a) in situ HOC concentration gradients measured with passive samplers and (b) mass transfer coefficients measured with a novel flux method using Empore disks. For eight undisturbed sediments, this method identified whether the sediment acted as a source or as a sink for HOCs. The analysis also identified which type of transport resistance governed sediment water exchange. For seven inland locations, exchange was limited by benthic boundary layer transport, showing no dependencies on sediment or chemical properties other than concentration. For one river mouth location, exchange was limited by slow in-bed intraparticle diffusion. A biphasic dual compartment radial diffusion model adequately described the data for this location. Fast desorption was interpreted as molecular diffusion retarded by microscale dual domain sorption to amorphous as well as black carbon (BC). Slow desorption was invariant with LogK(ow) and consistent with intraorganic matter diffusion through BC particles. Finally, it is discussed how these findings can be translated into a general framework for flux based exposure assessment.

Measuring bioavailability: from a scientific approach to standard methods.

Biological effects are not related to the total concentration of a contaminant in the soil and soil-like materials. Organisms respond only to the fraction that is biologically available. The bioavailable fractions of contaminants are dependent on soil properties and various processes varying with time and on the behavior or the target organism. Bioavailability may be assessed in two complementary ways: (i) by chemical methods (e.g., extraction methods), which determine a defined available fraction of a well defined class of contaminants; and (ii) by biological methods, which expose organisms to soil or soil eluates to monitor effects. Although there is scientific discussion on the concept of bioavailability, the literature gives enough evidence to recognize bioavailability as a promising tool in risk assessment. A large number of methods are available. Under regulatory aspects of soil protection, a risk assessment should be based on the same common concept of determination and assessment of exposure and measuring and assessment of effects. A harmonized framework on bioavailability is necessary to promote the development and introduction of workable (international) standard methods to be used in soil and site assessment. The working group 'Bioavailability' of ISO/TC190-Soil Quality has developed a guidance document for development and selection of methods to assess bioavailability for different target species with regard to several classes of contaminants. The way to this standard, on the border of science and regulation, is described in this article.

Oil effect in freshly spiked marine sediment on Vibrio fischeri, Corophium volutator, and Echinocardium cordatum.

The purpose of this study was to provide data to be used in The Netherlands for development of ecotoxicologically based quality criteria for oil-contaminated sediments and dredged material. In addition, the relation of toxicity to specific oil boiling-point fraction ranges was explored. Natural marine sediment, with a moisture, organic carbon, and silt content of approximately 80, 1.8, and 33% of the dry weight, respectively, was artificially spiked using a spiking method developed in this project. Aliquots of one part of the sediment were spiked to several concentrations of Gulf distillate marine grade A (DMA) gasoil (containing 64% C10-19) and aliquots of the other part to several concentrations of Gulf high viscosity grade 46 (HV46) hydraulic oil (containing 99.2% C19-40). Thus, for each individual oil type, a concentration series was created. Vibrio fischeri (endpoint: bioluminescence inhibition), Corophium volutator (endpoint:mortality), and Echinocardium cordatum (endpoint:mortality) were exposed to these spiked sediments for 10 min, 10 d and 14 d, respectively. Based on the test results, the effective concentration on 50% of the test animals was statistically estimated. For DMA gasoil and HV46 hydraulic oil, respectively, the effective concentrations were 43.7 and 2,682 mg/kg dry weight for V. fischeri, 100 and 9,138 mg/kg dry weight for C. volutator, 190, and 1064 mg/kg dry weight for E. cordatum. This study shows that the toxicity is strongly correlated with the lower boiling-point fractions and especially to those within the C10-C19 range.