Low soil Moisture Slows Uptake and Elimination Rates of Phenanthrene in Springtails.

This study investigated the influence of soil water status on the toxicokinetics of phenanthrene in the springtail Folsomia candida allowing estimation of uptake and elimination rates at two contrasting soil water potentials. Fitting a three-phase model to the observations showed that uptake rate (ku) was almost two times higher in moist soil (-2 kPa) than in dry soil (-360 kPa). During the first days of the exposure, elimination rate (ke) was not significantly different in moist and dry soil, but after eight days ke had increased significantly more in moist soil than in dry soil. Our results confirm the general notion that the exposure route via soil pore water is important. Understanding the significance of soil moisture in exposure and effects of contaminants on soil invertebrates is crucial for assessing the ecological risks associated with soil pollution in a changing climate.

Regulated and Unregulated Halogenated Flame Retardants in Peregrine Falcon Eggs from Greenland.

Median levels of regulated flame retardants, i.e., polybrominated diphenyl ethers (PBDEs), brominated biphenyl (BB)-153, and hexabromocyclododecane (HBCD), in 33-48 eggs of peregrine falcons (Falco peregrinus) from Greenland were 1909, 359, and 5.98 ng/g lipid weight (lw), respectively, and generally intermediate to levels in North America and Europe. Unregulated flame retardants had lower median concentrations of 1.06 (2-ethylhexyl-2,3,4,5-tetrabromobenzoate, EH-TBB), 2.42 (1,2-bis(2,4,6-tribromophenoxy)-ethane, BTBPE), 0.52 (2,4,6-tribromophenyl 2,3-dibromopropyl ether, DPTE), and 4.78 (dechlorane plus) ng/g lw. Although these compounds are often described as recent replacements for PBDEs, they were also present in eggs from the 1980s. BDE-209 was the only compound with a significant increase (+7.2% annual change) between 1986 and 2014, while BB-153 and DPTE decreased significantly (-8.0% and -2.8% annual change, respectively). Dechlorane plus showed a nonsignificant increase. Individual birds, equipped with light-logging geolocators, confirmed the contaminant exposure over a large geographical area as the birds spent nearly equal time periods in their breeding and wintering grounds in Greenland and Central/South America, respectively, interrupted by 5-6 weeks of migration through North America.

Implementing the DF4 in a robust model, allowing for enhanced comparison, prioritisation and grouping of Nanomaterials.

It is here shown how partial order can be used to provide a robust and consistent implementation of the DF4 approach which provides unbiased information enabling comparison and open up the possibility for grouping. The approach is based on few assumptions, works well with the data, can include different types of input parameters, and can provide fundamental information about the ranks of tested materials. It is shown that the materials in many cases are below one threshold within a tier, but above another threshold within the same tier. It is also observed that the ranks of the materials can differ between tiers, although this is less relevant for DF4 since parameters evaluation may be hierarchical.

An Integrated Data-Driven Strategy for Safe-by-Design Nanoparticles: The FP7 MODERN Project.

The development and implementation of safe-by-design strategies is key for the safe development of future generations of nanotechnology enabled products. The safety testing of the huge variety of nanomaterials that can be synthetized is unfeasible due to time and cost constraints. Computational modeling facilitates the implementation of alternative testing strategies in a time and cost effective way. The development of predictive nanotoxicology models requires the use of high quality experimental data on the structure, physicochemical properties and bioactivity of nanomaterials. The FP7 Project MODERN has developed and evaluated the main components of a computational framework for the evaluation of the environmental and health impacts of nanoparticles. This chapter describes each of the elements of the framework including aspects related to data generation, management and integration; development of nanodescriptors; establishment of nanostructure-activity relationships; identification of nanoparticle categories; hazard ranking and risk assessment.

NORMA-Gene: a simple and robust method for qPCR normalization based on target gene data.

BACKGROUND: Normalization of target gene expression, measured by real-time quantitative PCR (qPCR), is a requirement for reducing experimental bias and thereby improving data quality. The currently used normalization approach is based on using one or more reference genes. Yet, this approach extends the experimental work load and suffers from assumptions that may be difficult to meet and to validate. RESULTS: We developed a data driven normalization algorithm (NORMA-Gene). An analysis of the performance of NORMA-Gene compared to reference gene normalization on artificially generated data-sets showed that the NORMA-Gene normalization yielded more precise results under a large range of parameters tested. Furthermore, when tested on three very different real qPCR data-sets NORMA-Gene was shown to be best at reducing variance due to experimental bias in all three data-sets compared to normalization based on the use of reference gene(s). CONCLUSIONS: Here we present the NORMA-Gene algorithm that is applicable to all biological and biomedical qPCR studies, especially those that are based on a limited number of assayed genes. The method is based on a data-driven normalization and is useful for as little as five target genes comprising the data-set. NORMA-Gene does not require the identification and validation of reference genes allowing researchers to focus their efforts on studying target genes of biological relevance.

Human health risk screening due to consumption of fish contaminated with chemical warfare agents in the Baltic Sea.

Chemical warfare agents (CWAs) have been disposed of in various fashions over the past decades. Significant amounts of CWA, roughly 11,000ton, have been dumped in the Baltic Sea east of the island Bornholm following the disarmament of Germany after World War II. This has caused concerns over potential human and environmental health risks, and resulted in restrictions on fishing in the dumpsite area. The purpose of this paper is to assess the potential indirect human health risks due to consumption of CWA-contaminated fish from the dumpsite area east of Bornholm. Earlier studies suggest that the fish community may be at risk from CWA exposure in the Bornholm basin. Moreover, elevated frequencies of lesions on fish caught in a CWA dumpsite in the Mediterranean Sea have been observed. The fish at the Mediterranean dumpsite had elevated total arsenic (As) concentrations in their tissue, and elevated total As levels were also observed in the sediment. Elevated total sediment As concentrations have also been recorded in CWA dumpsites in the Skagerrak and the Baltic Sea. Triphenylarsine and sulfur mustard gas (Yperite) are the CWAs with the greatest indirect human health risk potential. There are recognized uncertainties concerning Yperite's and CWA-derived arsenical's fate and speciation in the environment, as well as their inherent toxicity, warranting caution and further site-specific environmental and human health risk assessments of CWAs dumped in the Bornholm basin.

Perfluoroalkyl substances (PFASs) and polychlorinated naphthalenes (PCNs) add to the chemical cocktail in peregrine falcon eggs.

A suite of perfluoroalkyl substances (PFASs) and polychlorinated naphthalenes (PCNs) were determined in 41 peregrine falcon eggs collected in South Greenland between 1986 and 2014. Median concentrations of perfluorinated sulfonic acids (ΣPFSA) and perfluorinated carboxylic acids (ΣPFCA) were 303 ng/g dry weight (dw) (58 ng/g wet weight, ww) and 100 ng/g dw (19 ng/g ww), respectively, which was comparable to other studies. Perfluorooctane sulfonate (PFOS) accounted for 94% on average of all PFSAs, but did not show a significant time trend. Perfluorohexane sulfonate (PFHxS), perfluoroheptane sulfonate (PFHpS) and perfluorodecane sulfonate (PFDS) showed non-linear decreases over the study period, while some long-chain PFCAs increased significantly. The PCN profile was dominated by the penta-, hexa- and tetrachlorinated congeners CN-52/60, CN-66/67 and CN-42. CN-54, an indicator of combustion, accounted for 2.4% of ΣPCN on average. All PCN congeners showed a decreasing tendency, which was significant for lipid-normalized concentrations of CN-53, CN-54 and CN-63. The ΣPCN median concentration was 21 ng/g lipid weight, which is in the high end of concentrations reported for bird eggs. The PCN and PFAS concentrations add to an already high contaminant burden and a complex chemical cocktail in the peregrine falcon population in Greenland, mainly reflecting contaminant exposure during migration and winter stays in Central and South America.

Screening level fish community risk assessment of chemical warfare agents in the Baltic Sea.

Chemical warfare agents (CWAs) have been disposed of in various fashions over the past decades. Significant amounts (approximately 11,000 tonnes) have been dumped in the Baltic Sea east of the island Bornholm following the disarmament of Germany after World War II, causing concerns over potential environmental risks. Absence of risk based on assumptions of extremely low solubility of CWAs cannot alone dismiss these concerns. Existing and modelled fate and effects data were used in the analysis to assess the fish community risk level. The most realistic and also conservative assessment result is the scenario describing 70 m water depth for the most realistic dump-site area with a focus on chronic toxicity, at 0-20 cm above the sediment, yielding a total mixture toxic unit (TU) of 0.62. Triphenylarsine is the CWA with the highest realistic risk profile at 0.2 TU for the fish community followed by Adamsite (0.17), Clark I (0.086) and Yperite (0.083) TU. Adamsite is more persistent and constitutes a potential risk for a longer period than triphenylarsine. The seawater volume potentially at risk is <4 m above sediment and <58 km down current of dump sites. Further risk assessment of dumped CWAs in the Baltic Sea is warranted.

PBT screening profile of chemical warfare agents (CWAs).

Chemical warfare agents (CWAs) have been used and disposed of in various fashions over the past decades. Significant amounts have been dumped in the Baltic Sea following the disarmament of Germany after World War II causing environmental concerns. There is a data gap pertaining to chemical warfare agents, environmental properties not the least their aquatic toxicities. Given this gap and the security limitations relating to working with these agents we applied Quantitative Structure-Activity Relationship ((Q)SAR) models in accordance with the European Technical Guidance Document (2003) to 22 parent CWA compounds and 27 known hydrolysis products. It was concluded that conservative use of EPI Suite (Q)SAR models can generate reliable and conservative estimations of chemical warfare agents acute aquatic toxicity. From an environmental screening point of view the organoarsenic chemical warfare agents Clark I and Adamsite comprise the most problematic of the screened CWA compounds warranting further investigation in relation to a site specific environmental risk assessment. The mustard gas agents (sulphur and nitrogen) and the organophosphorous CWAs (in particular Sarin and Soman) are a secondary category of concern based upon their toxicity alone. The undertaken approach generates reliable and conservative estimations for most of the studied chemicals but with some exceptions (e.g. the organophosphates).

Sugar and amino acid preference in the black garden ant Lasius niger (L.).

The mutualistic relationship that the garden ant Lasius niger (L.) establishes with trophobiotic homopterans makes this ant an unwelcome host in commercial crops, as ants improve the survival of homopteran pests from which they collect honeydew as a source of carbohydrates. Because the offering of alternative sugar sources can be used to disrupt this relationship, the present study explored L. niger's preference towards sugar and amino acid components that may be used in sugar solutions to increase their attractiveness. We tested the ant's preference between basic sugars (mono- and disaccharides) used as main ingredients and attractants (trisaccharides and amino acid (AA) sources) added to basic sugar in small amounts. Results showed that ants preferred disaccharides over monosaccharides, and that trisaccharides increased the attractiveness of sucrose solutions, albeit not when a protein source was added to the mix. In the case of AA sources, ants preferred components with a more diverse composition. In conclusion, trisaccharides and AA sources can be used to increase the attractiveness of sugar solutions, leading to the development of solutions that when supplied in artificial feeders can out-compete honeydew and disrupt harmful ant-homopteran mutualisms in agriculture.

Risk of five polycyclic aromatic hydrocarbons in a terrestrial environment: influence of data variability.

The risk of five different pyrogenic polycyclic aromatic hydrocarbons (PAHs) toward two soil-dwelling organisms (i.e., springtail [Folsomia fimetaria] and earthworm [Eisenia veneta]) has been investigated with respect to lethality and reproduction at two soil depths in a typical Danish soil. Predicted environmental concentrations (PECs) are calculated with a model describing diffusion, bulk flow, and microbial degradation. Predicted no-effect concentrations (PNECs) are derived from laboratory experiments performed with nominal soil concentrations in the range from 0 to 300 microg PAH/g dry weight. Risk is estimated through a stochastic approach as well as with the conventional point estimate. The point estimate predicts a potential risk for pyrene, log PEC/PNEC = -0.01, with respect to springtail reproduction at 5 cm soil depth. In all other scenarios, the point-estimate log-ratios are significantly lower than 0. For the stochastic approach risk is defined when the probability for risk (i.e., the probability for log PEC/PNEC > 0), is larger than 5%. The results show that risk is present only for springtail and in the following five scenarios: For anthracene, the probability for risk with respect to lethality is 12% at 5 cm soil depth, and 17 and 5% with respect to reproduction at 5 and 50 cm soil depth, respectively; for pyrene the probability for risk with respect to reproduction is 49 and 14% at 5 and 50 cm, respectively. The results show that risk cannot be defined unambiguously with the two approaches. The probabilistic approach is less restrictive, and even small probabilities may be used as early-warning indications that risk may be posed under unfavorable circumstances.

Phthalates, nonylphenols and LAS in an alternately operated wastewater treatment plant--fate modelling based on measured concentrations in wastewater and sludge.

The performance of an alternately operated activated sludge wastewater treatment plant (WWTP) has been investigated with respect to six phthalates, nonylphenol (NP) and nonylphenol diethoxylate (NPDE) and linear alkylbenzene sulphonates (LAS). Samples of raw sewage, primary and secondary sludge and treated water were collected during an 8-day period in May 1999 and analysed for dissolved and sorbed substances. To evaluate the system performance with respect to substance removal through biodegradation and sorption to sludge the measured data were applied in a model describing the different bioreactors as one single reactor, corresponding to the concepts of, e.g. SimpleTreat. The most abundant of the investigated phthalates was di-(2-ethylhexyl)-phthalate (DEHP) with a measured mean inlet flow of 240g/day. Two percent of this amount was found in the treated water, 70% was biodegraded and 28% was found in the sludge. For LAS the mean inlet flow was 20,300g/day, of which less than 1% was found in the treated water, 84% was biodegraded and 15% was found in the sludge. The mean inlet flow of NP and NPDE was 44 and 590g/day, of which 4% and 2% was found in the treated water, 80% was biodegraded for both substances, and 16% and 18% was found in the sludge, respectively. The WWTP removal of the investigated substances was thus high compared to other studies of conventional activated sludge WWTPs. The simple model set-up presents a strong tool for predicting substance removal and system sensitivity related to changes in the inlet conditions, such as concentrations and flow. Furthermore, it allows the inclusion of complex alternately operated WWTPs in risk assessment tools such as e.g. SimpleTreat.

Evaluation of the ranking probabilities for partial orders based on random linear extensions.

Partial order theory and Hasse diagrams appears to be a promising tool for decision-making in environmental issues. Alternatives or objects are said to be partial ordered when it is impossible to find a mutual relationship (< or >) for all criteria. This is often the case in complicated real life situations. However, sometimes it is attractive to apply a total order, i.e. linear rank, and not just the partial order. Based on ranking probabilities and linear extensions it is possible to derive a total order. A linear extension is a projection of the partial order into a total order that comply with all the relations in the partial order. When all linear extensions are known the ranking probabilities can be found as the probability for an object to occupy a specific rank. However, the total number of linear extensions is proportional with the faculty of the number of objects in the partial order. Therefore it is practically impossible to identify all possible linear extensions for partial orders with more than around 20 objects. This study reviews and evaluates a method which estimates the ranking probability based on sampling of a minor random fraction of the linear extensions. Using standard statistics the necessary number of random linear extensions is described as a function of the ranking probability estimate and the restrictions on the confidence interval around the ranking probability. The analysis reveals a smaller systematic uncertainty, which occurs due to the random selection of ranking between two incomparable objects. The discrepancy appears to be dependent on the structure of the partial order. The method using random linear extensions thus appears as a valuable tool for analysing larger partially ordered sets, which are practically impossible to handle using the total set of linear extensions.

Model description of an alternately operated wastewater treatment plant--evaluation of the applicability of SimpleTreat.

Alternately operated wastewater treatment plants (WWTPs) are fundamentally different compared to conventional activated sludge WWTPs with respect to flow patterns and aeration in the biological reactors. Several model applications exist for conventional WWTPs, e.g. SimpleTreat, and in this study the effect of substituting a complex discontinuous operation, involving alternating degradation and flow conditions between two reactors, with one single bioreactor with continuos flow (SimpleTreat) has been investigated by setting up two models representing the respective operation schemes. The discontinuous operation induces fluctuations in the outlet concentrations that are not modelled with the single bioreactor model, however, the fluctuations and the associated uncertainties were found to be insignificant compared to the influence of the input parameter uncertainties on the model results. An empirical relationship between an aggregate pseudo-1st order degradation rate for the single bioreactor model and realistic aerobic and anoxic 1st order degradation rates, respectively, has been established. When using this aggregate degradation rate in the single bioreactor model an outlet concentration can be calculated that deviates no more than 2% from the mean outlet concentration from the alternating operation model. For substances with aerobic half-lives longer than approximately 2 h, which is valid for many chemical substances, the aggregate 1st order degradation rate can be set equal to the aerobic 1st order degradation rate.

Comparison of the combined monitoring-based and modelling-based priority setting scheme with partial order theory and random linear extensions for ranking of chemical substances.

The combined monitoring-based and modelling-based priority setting scheme (COMMPS) used to establish a priority setting list within the EU Water Framework Directive plays a major role in the European environmental policy on chemical substances. The COMMPS procedure can be classified as a so-called scoring method. The applied functional relationship and weight factors are established based on expert judgement, which unfortunately appears to be vulnerable to subjective inputs. In this study an alternative priority setting methods based on partial order theory (POT) and random linear extensions (RLE) is suggested and compared to the COMMPS procedure. The POT/RLE is characterised as being based on fewer assumptions concerning functional relationships and does not apply weighting factors. Using the POT/RLE methodology a different ranking result occur than when using the COMMPS procedure. Eight of the top 20 substances from the COMMPS procedure are not ranked within the top 20 when using POT/RLE. From the viewpoint of environmental protection, especially the substances that have been given low priority in the COMMPS procedure, but a high rank in POT/RLE, are of interest in a regulatory context. These substances are naphthalene, trichloromethane, isoproturon, metolachlor, endosulfan, acenaphthene, alachlor and dichloromethane. An analysis of the ability of the descriptors to separate the single substance discloses that the most significant descriptor is the concentrations detected in the environment. Further, the frequency of detection is not applied as a descriptor in the COMMPS procedure. However, if this descriptor was to be applied the analysis revealed that it would have been the third most significant descriptor.

Ranking of chemical substances based on the Japanese Pollutant Release and Transfer Register using partial order theory and random linear extensions.

In 1997 a Pollutant Release and Transfer Register (PRTR) pilot project was initiated in Japan. In 1998 the project was expanded and in 1999 a law concerning the establishment of a national PRTR was adopted. Data on the emissions of chemical substances are therefore now being reported on a continuous base. In relation to the PRTR project data on toxicity have been collected. In order to make efficient use of the collected information on emission and toxicity it is useful to group or rank the chemical substances according to the impact on human health and the environment. It has recently been argued that partial order theory (POT) in combination with the use of linear extensions (LE) may be the most objective way to create a linear rank. The methodology has been further expanded to handle larger data sets by the use of random linear extensions (RLE). In this paper the Japanese PRTR data are ranked using the POT/RLE methodology. An average rank is established for chemical substances in the 1998 and 1999 PRTR in Japan. The top 10 chemical substances in the 1998 PRTR are: dichlorvos, inorganic arsenic compounds, cobalt compounds, beryllium compounds, fenitrothion, disulfoton, parathion, diazinon, 4,4'-diamino-3,3'-dichlorodiphenylmethane and antimony compounds. The top 10 chemical substances from the 1999 PRTR are PCBs, lead compounds, fenitrothion, dichlorvos, disulfoton, inorganic arsenic compounds, chlorothalonil, thiobencarb, chromium and HCFC-141b. The descriptor having the highest influence on the ranking of the 1998 PRTR data is the production volume, which, however, is not given in the 1999 PRTR. Further, the disagreement between the ranking with the lack of toxicity data substituted with mean and maximum values, respectively, strongly indicates a general need for further toxicological investigations.

Ranking contaminated sites using a partial ordering method.

In this project, we apply the method of partial ordering on the ranking of 74 contaminated sites located in the county of West Zealand (Denmark). The method is based on the concept that the parameters are kept separated through the ranking analysis, and thus no weighing of the different parameter values is necessary. The ranking is displayed in a graphical form by the Hasse diagram technique to ease the interpretation. A critical comparison is made of the ranking of contaminated sites by the partial ordering method and an index function used by the county of West Zealand. Comparing the ranking by the partial ordering method to the index function shows that the choice of score points and index function highly influences the ranking result, as only four sites are equally ranked. The importance of the parameters used to identify the environmental hazard of the contaminated sites is analyzed in order to evaluate the influence of each parameter on the ranking. From among a total of six different parameters, two have high influence, two medium, and two low because of both the construction of the scoring system and the characteristics of the data.

Analysis of monitoring data of pesticide residues in surface waters using partial order ranking theory.

In this investigation, a new and simple way to analyze, interpret, and generalize monitoring data of occurrence of pesticide active ingredients in surface waters was developed. The occurrence is quantified using the variables frequency of detection and the concentration level. These two parameters are associated with basically different ecotoxicological effects; for example, a high frequency of detection may be related to bioaccumulation problems, while the level of concentration also controls the acute toxicological effects. The active ingredients were ranked on the basis of the monitoring data in relation to both the frequency of finding and concentration level using the concept of partial ordered sets. The resulting rankings was correlated with other rankings based on descriptors such as sprayed area, applied dose, adsorption to soil organic carbon, vapor pressure, and soil dissipation half-life. A similarity index was applied in order to compare the ranking of the monitoring data with the ranking of the descriptors. It is shown how partial order theory can be used to evaluate the relevance of every single descriptor. The dosage is found to be the most important descriptor, followed by the sprayed area and the adsorption to organic carbon ending up a very close similarity between, respectively, the rankings using monitoring data and rankings using these three descriptors.

Levels and trends of toxaphene and chlordane-related pesticides in peregrine falcon eggs from South Greenland.

Peregrine falcon eggs were collected in South Greenland between 1986 and 2003 and analysed for 6 congeners of toxaphene and 5 chlordane-related pesticides (cis-chlordane, trans-chlordane, cis-nonachlor, trans-nonachlor and oxychlordane). Oxychlordane had the highest median concentration of 1448 ng/g lipid weight (lw) or 79 ng/g wet weight (ww) of all compounds. Of the toxaphene congeners, CHB-50 was the predominant congener, with a median concentration of 215 ng/g lw (15.5 ng/g ww). Chlordane-related concentrations were comparable with results from the USA, but lower than those from Canada and Norway. Toxaphene was considerably higher than in eggs of Norwegian peregrine falcon eggs, possibly reflecting different toxaphene usage in the areas of peregrine falcon migration. Toxaphene information in birds of prey is limited and comparisons with other species indicate differences in concentrations and organochlorine pattern. Temporal trends showed significant log-linear decreases for cis-chlordane and trans-chlordane, but no significant trends for other chlordanes or the toxaphene congeners, probably affected by the large variation between eggs, also of the same bird. Correlations between chlordanes and toxaphene in the Greenland peregrine falcon eggs might suggest similar sources of exposure.

Conceptual modeling for identification of worst case conditions in environmental risk assessment of nanomaterials using nZVI and C60 as case studies.

Conducting environmental risk assessment of engineered nanomaterials has been an extremely challenging endeavor thus far. Moreover, recent findings from the nano-risk scientific community indicate that it is unlikely that many of these challenges will be easily resolved in the near future, especially given the vast variety and complexity of nanomaterials and their applications. As an approach to help optimize environmental risk assessments of nanomaterials, we apply the Worst-Case Definition (WCD) model to identify best estimates for worst-case conditions of environmental risks of two case studies which use engineered nanoparticles, namely nZVI in soil and groundwater remediation and C(60) in an engine oil lubricant. Results generated from this analysis may ultimately help prioritize research areas for environmental risk assessments of nZVI and C(60) in these applications as well as demonstrate the use of worst-case conditions to optimize future research efforts for other nanomaterials. Through the application of the WCD model, we find that the most probable worst-case conditions for both case studies include i) active uptake mechanisms, ii) accumulation in organisms, iii) ecotoxicological response mechanisms such as reactive oxygen species (ROS) production and cell membrane damage or disruption, iv) surface properties of nZVI and C(60), and v) acute exposure tolerance of organisms. Additional estimates of worst-case conditions for C(60) also include the physical location of C(60) in the environment from surface run-off, cellular exposure routes for heterotrophic organisms, and the presence of light to amplify adverse effects. Based on results of this analysis, we recommend the prioritization of research for the selected applications within the following areas: organism active uptake ability of nZVI and C(60) and ecotoxicological response end-points and response mechanisms including ROS production and cell membrane damage, full nanomaterial characterization taking into account detailed information on nanomaterial surface properties, and investigations of dose-response relationships for a variety of organisms.