Relationship between Composition and Environmental Degradation of Poly(isosorbide-co-diol oxalate) (PISOX) Copolyesters.

To reduce the global CO2 footprint of plastics, bio- and CO2-based feedstock are considered the most important design features for plastics. Oxalic acid from CO2 and isosorbide from biomass are interesting rigid building blocks for high Tg polyesters. The biodegradability of a family of novel fully renewable (bio- and CO2-based) poly(isosorbide-co-diol) oxalate (PISOX-diol) copolyesters was studied. We systematically investigated the effects of the composition on biodegradation at ambient temperature in soil for PISOX (co)polyesters. Results show that the lag phase of PISOX (co)polyester biodegradation varies from 0 to 7 weeks. All (co)polyesters undergo over 80% mineralization within 180 days (faster than the cellulose reference) except one composition with the cyclic codiol 1,4-cyclohexanedimethanol (CHDM). Their relatively fast degradability is independent of the type of noncyclic codiol and results from facile nonenzymatic hydrolysis of oxalate ester bonds (especially oxalate isosorbide bonds), which mostly hydrolyzed completely within 180 days. On the other hand, partially replacing oxalate with terephthalate units enhances the polymer's resistance to hydrolysis and its biodegradability in soil. Our study demonstrates the potential for tuning PISOX copolyester structures to design biodegradable plastics with improved thermal, mechanical, and barrier properties.

Pilot-scale hybrid constructed wetlands for the treatment of cooling tower water prior to its desalination and reuse.

Cooling towers are responsible for a large part of the industrial fresh water withdrawal, and the reuse of cooling tower water (CTW) effluents can strongly lower industrial fresh water footprints. CTW requires desalination prior to being reused, but various CTW components, such as total organic carbon (TOC), conditioning chemicals and total suspended solids (TSS) hamper physico-chemical desalination technologies and need to be removed from the CTW. A cost-efficient and robust pre-treatment is thus required, which can be provided by constructed wetlands (CWs). The present study is the first study that determined the CTW pre-treatment efficiency of hybrid-CWs and the impact of winter season and biocides in the CTW on the pre-treatment efficiency. The most efficient CW flow type and dominant removal mechanisms for CW components hampering physico-chemical desalination were determined. Subsurface flow CWs removed PO43-, TSS and TOC as a result of adsorption and filtration. Vertical subsurface flow CWs (VSSF-CW) excelled in the removal of benzotriazole as a result of aerobic biodegradation. Horizontal subsurface flow CWs (HSSF-CW) allowed the denitrification of NO3- due to their anaerobic conditions. Open water CWs (OW-CWs) did not contribute to the removal of components that hamper physico-chemical desalination technologies, but do provide water storage options and habitat. The biological removal processes in the different CW flow types were negatively impacted by the winter season, but were not impacted by concentrations of the biocides glutaraldehyde and DBNPA that are relevant in practice. For optimal pre-treatment, a hybrid-CW, consisting of an initial VSSF-CW followed by an OW-CW and HSSF-CW is recommended. Future research should focus on integrating the hybrid-CW with a desalination technology, e.g. reverse osmosis, electrodialysis or capacitive ionization, to produce water that meets the requirements for use as cooling water and allow the reuse of CTW in the cooling tower itself.

A Nondestructive Method to Identify POP Contamination Sources in Omnivorous Seabirds.

Persistent organic pollutants (POPs) are present in almost all environments due to their high bioaccumulation potential. Especially species that adapted to human activities, like gulls, might be exposed to harmful concentrations of these chemicals. The nature and degree of the exposure to POPs greatly vary between individual gulls, due to their diverse foraging behavior and specialization in certain foraging tactics. Therefore, in order clarify the effect of POP-contaminated areas on gull populations, it is important to identify the sources of POP contamination in individual gulls. Conventional sampling methods applied when studying POP contamination are destructive and ethically undesired. The aim of this literature review was to evaluate the potential of using feathers as a nondestructive method to determine sources of POP contamination in individual gulls. The reviewed data showed that high concentrations of PCBs and PBDEs in feathers together with a large proportion of less bioaccumulative congeners may indicate that the contamination originates from landfills. Low PCB and PBDE concentrations in feathers and a large proportion of more bioaccumulative congeners could indicate that the contamination originates from marine prey. We propose a nondestructive approach to identify the source of contamination in individual gulls based on individual contamination levels and PCB and PBDE congener profiles in feathers. Despite some uncertainties that might be reduced by future research, we conclude that especially when integrated with other methods like GPS tracking and the analysis of stable isotopic signatures, identifying the source of POP contamination based on congener profiles in feathers could become a powerful nondestructive method.

Biodegradation of metformin and its transformation product, guanylurea, by natural and exposed microbial communities.

Metformin (MET) is a pharmaceutical product mostly biotransformed in the environment to a transformation product, guanylurea (GUA). In ready biodegradability tests (RBTs), however, contrasting results have been observed for metformin. The objective of this study was to measure the biodegradation of MET and GUA in RBTs, using activated sludge from the local wastewater treatment plant, either directly or after pre-exposure to MET, in a chemostat. The activated sludge community was cultivated in chemostats, in presence or absence of MET, for a period of nine months, and was used in RBT after one, three and nine months. The results of this study showed that the original activated sludge was able to completely remove MET (15 mg/l) and the newly produced GUA (50% of C0MET) under the test conditions. Inoculation of the chemostat led to a rapid shift in the community composition and abundance. The community exposed to 1.5 mg/l of MET was still able to completely consume MET in the RBTs after one-month exposure, but three- and nine-months exposure resulted in reduced removal of MET in the RBTs. The ability of the activated sludge community to degrade MET and GUA is the result of environmental exposure to these chemicals as well as of conditions that could not be reproduced in the laboratory system. A MET-degrading strain belonging to the genus Aminobacter has been isolated from the chemostat community. This strain was able to completely consume 15 mg/l of MET within three days in the test. However, community analysis revealed that the fluctuation in relative abundance of this genus (<1%) could not be correlated to the fluctuation in biodegradation capacity of the chemostat community.

Identification of Novel Brominated Compounds in Flame Retarded Plastics Containing TBBPA by Combining Isotope Pattern and Mass Defect Cluster Analysis.

The study of not only main flame retardants but also of related degradation products or impurities has gained attention in the last years and is relevant to assess the safety of our consumer products and the emission of potential contaminants into the environment. In this study, we show that plastics casings of electric/electronic devices containing TBBPA contain also a complex mixture of related brominated chemicals. These compounds were most probably coming from impurities, byproducts, or degradation products of TBBPA and TBBPA derivatives. A total of 14 brominated compounds were identified based on accurate mass measurements (formulas and tentative structures proposed). The formulas (or number of bromine elements) for 19 other brominated compounds of minor intensity are also provided. A new script for the recognition of halogenated compounds based on combining a simplified isotope pattern and mass defect cluster analysis was developed in R for the screening. The identified compounds could be relevant from an environmental and industrial point of view.

Modelling the Release, Transport and Fate of Engineered Nanoparticles in the Aquatic Environment - A Review.

Engineered nanoparticles, that is, particles of up to 100 nm in at least one dimension, are used in many consumer products. Their release into the environment as a consequence of their production and use has raised concern about the possible consequences. While they are made of ordinary substances, their size gives them properties that are not manifest in larger particles. It is precisely these properties that make them useful. For instance titanium dioxide nanoparticles are used in transparent sunscreens, because they are large enough to scatter ultraviolet light but too small to scatter visible light.To investigate the occurrence of nanoparticles in the environment we require practical methods to detect their presence and to measure the concentrations as well as adequate modelling techniques. Modelling provides both a complement to the available detection and measurement methods and the means to understand and predict the release, transport and fate of nanoparticles. Many different modelling approaches have been developed, but it is not always clear for what questions regarding nanoparticles in the environment these approaches can be applied. No modelling technique can be used for every possible aspect of the release of nanoparticles into the environment. Hence it is important to understand which technique to apply in what situation. This article provides an overview of the techniques involved with their strengths and weaknesses. Two points need to be stressed here: the modelling of processes like dissolution and the surface activity of nanoparticles, possibly under influence of ultraviolet light, or chemical transformation has so far received relatively little attention. But also the uncertainties surrounding nanoparticles in general-the amount of nanoparticles used in consumer products, what constitutes the appropriate measure of concentration (mass or numbers) and what processes are relevant-should be explicitly considered as part of the modelling.

Effects of clay minerals, hydroxides, and timing of dissolved organic matter addition on the competitive sorption of copper, nickel, and zinc: A column experiment.

Infiltration of heavy metal (HM) polluted wastewater can seriously compromise soil and groundwater quality. Interactions between mineral soil components (e.g. clay minerals) and dissolved organic matter (DOM) play a crucial role in determining HM mobility in soils. In this study, the influence of the timing of addition of DOM, i.e. concurrent with or prior to HMs, on HM mobility was explored in a set of continuous flow column experiments using well defined natural soil samples amended with goethite, birnessite and/or smectite. The soils were subjected to concurrent and sequential additions of solutions of DOM, and Cu, Ni and Zn. The resulting breakthrough curves were fitted with a modified dose-response model to obtain the adsorption capacity (q0). Addition of DOM prior to HMs moderately enhanced q0 of Cu (8-25%) compared to a control without DOM, except for the goethite amended soil that exhibited a 10% reduction due to the blocking of binding sites. Meanwhile, for both Zn and Ni sequential addition of DOM reduced q0 by 1-36% for all tested soils due to preferential binding of Zn and Ni to mineral phases. In contrast, concurrent addition of DOM and HMs resulted in a strong increase of q0 for all tested metals and all tested soil compositions compared to the control: 141-299% for Cu, 29-102% for Zn and 32-144% for Ni. Our study shows that when assessing the impact of soil pollution through HM containing wastewater it is crucial to take into account the presence of DOM.

Metabolic Pathways for Degradation of Aromatic Hydrocarbons by Bacteria.

The aim of this review was to build an updated collection of information focused on the mechanisms and elements involved in metabolic pathways of aromatic hydrocarbons by bacteria. Enzymes as an expression of the genetic load and the type of electron acceptor available, as an environmental factor, were highlighted. In general, the review showed that both aerobic routes and anaerobic routes for the degradation of aromatic hydrocarbons are divided into two pathways. The first, named the upper pathways, entails the route from the original compound to central intermediate compounds still containing the aromatic ring but with the benzene nucleus chemically destabilized. The second, named the lower pathway, begins with ring de-aromatization and subsequent cleavage, resulting in metabolites that can be used by bacteria in the production of biomass. Under anaerobic conditions the five mechanisms of activation of the benzene ring described show the diversity of chemical reactions that can take place. Obtaining carbon and energy from an aromatic hydrocarbon molecule is a process that exhibits the high complexity level of the metabolic apparatus of anaerobic microorganisms. The ability of these bacteria to express enzymes that catalyze reactions, known only in non-biological conditions, using final electron acceptors with a low redox potential, is a most interesting topic. The discovery of phylogenetic and functional characteristics of cultivable and noncultivable hydrocarbon degrading bacteria has been made possible by improvements in molecular research techniques such as SIP (stable isotope probing) tracing the incorporation of (13)C, (15)N and (18)O into nucleic acids and proteins. Since many metabolic pathways in which enzyme and metabolite participants are still unknown, much new research is required. Therefore, it will surely allow enhancing the known and future applications in practice.

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.

Polyester biodegradability: importance and potential for optimisation.

To reduce global CO2 emissions in line with EU targets, it is essential that we replace fossil-derived plastics with renewable alternatives. This provides an opportunity to develop novel plastics with improved design features, such as better reusability, recyclability, and environmental biodegradability. Although recycling and reuse of plastics is favoured, this relies heavily on the infrastructure of waste management, which is not consistently advanced on a worldwide scale. Furthermore, today's bulk polyolefin plastics are inherently unsuitable for closed-loop recycling, but the introduction of plastics with enhanced biodegradability could help to combat issues with plastic accumulation, especially for packaging applications. It is also important to recognise that plastics enter the environment through littering, even where the best waste-collection infrastructure is in place. This causes endless environmental accumulation when the plastics are non-(bio)degradable. Biodegradability depends heavily on circumstances; some biodegradable polymers degrade rapidly under tropical conditions in soil, but they may not also degrade at the bottom of the sea. Biodegradable polyesters are theoretically recyclable, and even if mechanical recycling is difficult, they can be broken down to their monomers by hydrolysis for subsequent purification and re-polymerisation. Additionally, both the physical properties and the biodegradability of polyesters are tuneable by varying their building blocks. The relationship between the (chemical) structures/compositions (aromatic, branched, linear, polar/apolar monomers; monomer chain length) and biodegradation/hydrolysis of polyesters is discussed here in the context of the design of biodegradable polyesters.

Daphnid life cycle responses to new generation flame retardants.

Relatively hazardous brominated flame retardants (BFRs) are currently substituted with halogen-free flame retardants (HFFRs). Consequently, information on their persistence, bioaccumulation and toxicity (PBT) is urgently needed. Therefore, we investigated the chronic toxicity to the water flea Daphnia magna of two HFFRs, aluminum diethylphosphinate (ALPI) and 9,10-dihyro-9-oxa-10-phosphaphenanthrene-oxide (DOPO). The toxicity of ALPI increased from a 48 h LC50 of 18 mg L(-1) to a 21 day LC50 value of 3.2 mg L(-1), resulting in an acute-to-chronic ratio of 5.6. This may imply a change in classification from low to moderate toxicity. ALPI also affected sublethal life cycle parameters, with an EC50 of 2.8 mg L(-1) for cumulative reproductive output and of 3.4 mg L(-1) for population growth rate, revealing a nonspecific mode of action. DOPO showed only sublethal effects with an EC50 value of 48 mg L(-1) for cumulative reproductive output and an EC50 value of 73 mg L(-1) for population growth rate. The toxicity of DOPO to D. magna was classified as low and likely occurred above environmentally relevant concentrations, but we identified specific effects on reproduction. Given the low chronic toxicity of DOPO and the moderate toxicity of ALPI, based on this study only, DOPO seems to be more suitable than ALPI for BFR replacement in polymers.

Persistence, bioaccumulation, and toxicity of halogen-free flame retardants.

Polymers are synthetic organic materials having a high carbon and hydrogen content, which make them readily combustible. Polymers have many indoor uses and their flammability makes them a fire hazard. Therefore, flame retardants (FRs) are incorporated into these materials as a safety measure. Brominated flame retardants (BFRs), which accounted for about 21% of the total world market of FRs, have several unintended negative effects on the environment and human health. Hence, there is growing interest in finding appropriate alternative halogen-free flame retardants (HFFRs). Many of these HFFRs are marketed already, although their environ- mental behavior and toxicological properties are often only known to a limited extent, and their potential impact on the environment cannot yet be properly assessed. Therefore, we undertook this review to make an inventory of the available data that exists (up to September 2011) on the physical-chemical properties, pro- duction volumes, persistence, bioaccumulation, and toxicity (PBT) of a selection of HFFRs that are potential replacements for BFRs in polymers. Large data gaps were identified for the physical-chemical and the PBT properties of the reviewed HFFRs. Because these HFFRs are currently on the market, there is an urgent need to fill these data gaps. Enhanced transparency of methodology and data are needed to reevaluate certain test results that appear contradictory, and, if this does not provide new insights, further research should be performed. TPP has been studied quite extensively and it is clearly persistent, bioaccumulative, and toxic. So far, RDP and BDP have demonstrated low to high ecotoxicity and persistence. The compounds ATH and ZB exerted high toxicity to some species and ALPI appeared to be persistent and has low to moderate reported ecotoxicity. DOPO and MPP may be persistent, but this view is based merely on one or two studies, clearly indicating a lack of information. Many degradation studies have been performed on PER and show low persistence, with a few exceptions. Additionally, there is too l ittle information on the bioaccumulation potential of PER. APP mostly has low PBT properties; however, moderate ecotoxicity was reported in two studies. Mg(OH)2, ZHS, and ZS do not show such remarkably high bioaccumulation or toxicity, but large data gaps exist for these compounds also. Nevertheless, we consider the latter compounds to be the most promising among alternative HFFRs. To assess whether the presently reviewed HFFRs are truly suitable alternatives, each compound should be examined individually by comparing its PBT values with those of the relevant halogenated flame retardant. Until more data are available, it remains impossible to accurately evaluate the risk of each of these compounds, including the ones that are already extensively marketed.

Organic contaminants in bio-based fertilizer treated soil: Target and suspect screening approaches.

Using bio-based fertilizer (BBF) in agricultural soil can reduce the dependency on chemical fertilizer and increase sustainability by recycling nutrient-rich side-streams. However, organic contaminants in BBFs may lead to residues in the treated soil. This study assessed the presence of organic contaminants in BBF treated soils, which is essential for evaluating sustainability/risks of BBF use. Soil samples from two field studies amended with 15 BBFs from various sources (agricultural, poultry, veterinary, and sludge) were analyzed. A combination of QuEChERS-based extraction, liquid chromatography quadrupole time of flight mass spectrometry-based (LC-QTOF-MS) quantitative analysis, and an advanced, automated data interpretation workflow was optimized to extract and analyze organic contaminants in BBF-treated agricultural soil. The comprehensive screening of organic contaminants was performed using target analysis and suspect screening. Of the 35 target contaminants, only three contaminants were detected in the BBF-treated soil with concentrations ranging from 0.4 ng g-1 to 28.7 ng g-1; out of these three detected contaminants, two were also present in the control soil sample. Suspect screening using patRoon (an R-based open-source software platform) workflows and the NORMAN Priority List resulted in tentative identification of 20 compounds (at level 2 and level 3 confidence level), primarily pharmaceuticals and industrial chemicals, with only one overlapping compound in two experimental sites. The contamination profiles of the soil treated with BBFs sourced from veterinary and sludge were similar, with common pharmaceutical features identified. The suspect screening results suggest that the contaminants found in BBF-treated soil might come from alternative sources other than BBFs.

Simultaneous detection of pesticides and pharmaceuticals in three types of bio-based fertilizers by an improved QuEChERS method coupled with UHPLC-q-ToF-MS/MS.

Bio-based fertilizers (BBFs) have the potential to contain both pesticides and pharmaceutical residues, which may pose a threat to soils, crops, and human health. However, no analytical screening method is available currently to simultaneously analyze a wide range of contaminants in the complex origin-dependent matrices of BBFs. To fill this gap, our study tested and improved an original QuEChERS method (OQM) for simultaneously analyzing 78 pesticides and 18 pharmaceuticals in BBFs of animal, plant, and ashed sewage sludge origin. In spiked recovery experiments, 34-58 pharmaceuticals and pesticides were well recovered (recovery of 70-120%) via OQM at spiking concentrations levels of 10 ng/g and 50 ng/g in these three different types of BBFs. To improve the extraction efficiency further, ultrasonication and end-over-end rotation were added based on OQM, resulting in the improved QuEChERS method (IQM) that could recover 57-79 pesticides and pharmaceuticals, in the range of 70-120%. The detection limits of this method were of 0.16-4.32/0.48-12.97 ng/g, 0.03-11.02/0.10-33.06 ng/g, and 0.06-5.18/0.18-15.54 ng/g for animal, plant, and ash-based BBF, respectively. Finally, the IQM was employed to screen 15 BBF samples of various origins. 15 BBFs contained at least one pesticide or pharmaceutical with ibuprofen being frequently detected in at concentration levels of 4.1-181 ng/g. No compounds were detected in ash-based BBFs.

Risk reductions during pyrene biotransformation and mobilization in a model plant-bacteria-biochar system.

The productive application of motile microorganisms for degrading hydrophobic contaminants in soil is one of the most promising processes in modern remediation due to its sustainability and low cost. However, the incomplete biodegradation of the contaminants and the formation of the intermediary metabolites in the process may increase the toxicity in soil during bioremediation, and motile inoculants may mobilize the pollutants through biosorption. Therefore, controlling these factors should be a fundamental part of soil remediation approaches. The aim of this study was to evaluate the sources of risk associated with the cometabolism-based transformation of 14C-labeled pyrene by inoculated Pseudomonas putida G7 and identify ways to minimize risk. Our model scenario examined the increase in bioaccessibility to a distant source of contamination facilitated by sunflower (Helianthus annuus L.) roots. A biochar trap for mobilized pollutant metabolites and bacteria has also been employed. The experimental design consisted of pots filled with a layer of sand with 14C-labeled pyrene (88 mg kg-1) as a contamination focus located several centimeters from the inoculation point. Half of the pots included a biochar layer at the bottom. The pots were incubated in a greenhouse with sunflower plants and P. putida G7 bacteria. Pots with sunflower plants showed a higher biodegradation of pyrene, its mobilization as metabolites through the percolate and the roots, and bacterial mobilization toward the source of contamination, also resulting in increased pyrene transformation. In addition, the biochar layer efficiently reduced the concentrations of pyrene metabolites collected in the leachates. Therefore, the combination of plants, motile bacteria and biochar safely reduced the risk caused by the biological transformation of pyrene.

Plastics in the marine environment: the dark side of a modern gift.

Plastics are cheap, strong, and durable and offer considerable benefits to humanity. They potentially can enhance the benefits that both medical and scientific technology will bestow to humankind. However, it has now been several decades since the use of plastics exploded, and we have evidence that our current approach to production, use, transport and disposal of plastic materials has caused, and is still causing serious effects on wildlife, and is not sustainable. Because of frequent inappropriate waste management practices, or irresponsible human behavior, large masses of plastic items have been released into the environment, and thereby have entered the world's oceans. Moreover, this process continues, and in some places is even increasing. Most plastic debris that now exists in the marine environment originated from ocean-based sources such as the fishing industry. Plastics accumulate in coastal areas, at the ocean surface and on the seabed. Because 70% of all plastics are known to eventually sink, it is suspected that ever increasing amounts of plastic items are accumulating in seabed sediments. Plastics do not biodegrade, although, under the influence of solar UV radiations, plastics do degrade and fragment into small particles, termed microplastics. Our oceans eventually serve as a sink for these small plastic particles and in one estimate, it is thought that 200,000 microplastics per km(2) of the ocean's surface commonly exist. The impact of plastic debris has been studied since the beginning of the 1960's. To date, more than 267 species in the marine environment are known to have been affected by plastic entanglement or ingestion. Marine mammals are among those species that are most affected by entanglement in plastic debris. By contrast, marine birds suffer the most from ingestion of plastics. Organisms can also be seriously absorbed by floating plastic debris, or the contaminants may derive from plastic additives that are leached to the environment. Recent studies emphasize the important role of microplastics as they are easily ingestible by small organisms, such as plankton species, and form a pathway for contaminants to enter the food web. Contaminants leached from plastics tend to bioaccumulate in those organisms that absorb them, and chemical concentrations are often higher at higher trophic levels. This causes a threat to the basis of every food web and can have serious and far-reaching effects, even on nonmarine species such as polar bears and humans, who consume marine-grown food. Therefore, resolving the plastic debris problem is important to human kind for two reasons: we are both creator, and victim of the plastic pollution problem. Solutions to the plastic debris problem can only be achieved through a combination of actions. Such actions include the following: Legislation against marine pollution by plastics must be enforced, recycling must be accentuated, alternatives (biodegradable) to current plastic products must be found, and clean-up of debris must proceed, if the marine plastic pollution problem is to eventually be resolved. Governments cannot accomplish this task on their own, and will need help and initiative from the public. Moreover, resolving this long-standing problem will require time, money, and energy from many individuals now living and those of future generations, if a safer and cleaner marine environment is to be achieved.

Anaerobic degradation of benzene and other aromatic hydrocarbons in a tar-derived plume: Nitrate versus iron reducing conditions.

The anaerobic degradation of aromatic hydrocarbons in a plume originating from a Pintsch gas tar-DNAPL zone was investigated using molecular, isotopic- and microbial analyses. Benzene concentrations diminished at the relatively small meter scale dimensions of the nitrate reducing plume fringe. The ratio of benzene to toluene, ethylbenzene, xylenes and naphthalene (BTEXN) in the fringe zone compared to the plume zone, indicated relatively more loss of benzene in the fringe zone than TEXN. This was substantiated by changes in relative concentrations of BTEXN, and multi-element compound specific isotope analysis for δ2H and δ13C. This was supported by the presence of (abcA) genes, indicating the presumed benzene carboxylase enzyme in the nitrate-reducing plume fringe. Biodegradation of most hydrocarbon contaminants at iron reducing conditions in the plume core, appears to be quantitatively of greater significance due to the large volume of the plume core, rather than relatively faster biodegradation under nitrate reducing conditions at the smaller volume of the plume fringe. Contaminant concentration reductions by biodegradation processes were shown to vary distinctively between the source, plume (both iron-reducing) and fringe (nitrate-reducing) zones of the plume. High anaerobic microbial activity was detected in the plume zone as well as in the dense non aqueous phase liquid (DNAPL) containing source zone. Biodegradation of most, if not all, other water-soluble Pintsch gas tar aromatic hydrocarbon contaminants occur at the relatively large dimensions of the anoxic plume core. The highest diversity and concentrations of metabolites were detected in the iron-reducing plume core, where the sum of parent compounds of aromatic hydrocarbons was greater than 10 mg/L. The relatively high concentrations of metabolites suggest a hot spot for anaerobic degradation in the core of the plume downgradient but relatively close to the DNAPL containing source zone.

Biodegradability of novel high Tg poly(isosorbide-co-1,6-hexanediol) oxalate polyester in soil and marine environments.

In order to reduce the plastic accumulation in the environment, biodegradable plastics are attracting interest in the plastics market. However, the low thermal stability of most amorphous biodegradable polymers limits their application. With the aim of combining high glass transition temperature (Tg), with good (marine) biodegradation a family of novel fully renewable poly(isosorbide-co-diol) oxalate (PISOX-diol) copolyesters was recently developed. In this study, the biodegradability of a representative copolyester, poly(isosorbide-co-1,6-hexanediol) oxalate (PISOX-HDO), with 75/25 mol ratio IS/HDO was evaluated at ambient temperature (25 °C) in soil and marine environment by using a Respicond system with 95 parallel reactors, based on the principle of frequently monitoring CO2 evolution. During 50 days incubation in soil and seawater, PISOX-HDO mineralised faster than cellulose. The ready biodegradability of PISOX-HDO is related to the relatively fast non-enzymatic hydrolysis of polyoxalates. To study the underlying mechanism of PISOX-HDO biodegradation, the non-enzymatic hydrolysis of PISOX-HDO and the biodegradation of the monomers in soil were also investigated. Complete hydrolysis was obtained in approximately 120 days (tracking the formation of hydrolysis products via 1H NMR). It was also shown that (enzymatic) hydrolysis to the constituting monomers is the rate-determining step in this biodegradation mechanism. These monomers can subsequently be consumed and mineralised by (micro)organisms in the environment much faster than the polyesters. The combination of high Tg (>100 °C) and fast biodegradability is quite unique and makes this PISOX-HDO copolyester ideal for short term applications that demand strong mechanical and physical properties.

Scientific concepts and methods for moving persistence assessments into the 21st century.

The evaluation of a chemical substance's persistence is key to understanding its environmental fate, exposure concentration, and, ultimately, environmental risk. Traditional biodegradation test methods were developed many years ago for soluble, nonvolatile, single-constituent test substances, which do not represent the wide range of manufactured chemical substances. In addition, the Organisation for Economic Co-operation and Development (OECD) screening and simulation test methods do not fully reflect the environmental conditions into which substances are released and, therefore, estimates of chemical degradation half-lives can be very uncertain and may misrepresent real environmental processes. In this paper, we address the challenges and limitations facing current test methods and the scientific advances that are helping to both understand and provide solutions to them. Some of these advancements include the following: (1) robust methods that provide a deeper understanding of microbial composition, diversity, and abundance to ensure consistency and/or interpret variability between tests; (2) benchmarking tools and reference substances that aid in persistence evaluations through comparison against substances with well-quantified degradation profiles; (3) analytical methods that allow quantification for parent and metabolites at environmentally relevant concentrations, and inform on test substance bioavailability, biochemical pathways, rates of primary versus overall degradation, and rates of metabolite formation and decay; (4) modeling tools that predict the likelihood of microbial biotransformation, as well as biochemical pathways; and (5) modeling approaches that allow for derivation of more generally applicable biotransformation rate constants, by accounting for physical and/or chemical processes and test system design when evaluating test data. We also identify that, while such advancements could improve the certainty and accuracy of persistence assessments, the mechanisms and processes by which they are translated into regulatory practice and development of new OECD test guidelines need improving and accelerating. Where uncertainty remains, holistic weight of evidence approaches may be required to accurately assess the persistence of chemicals. Integr Environ Assess Manag 2022;18:1454-1487. © 2022 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).