Search

Infinite dilution partition coefficients, Kp,0, of a series of unbranched perfluoralkylacids, PFAAs with 3 to 8 CF2 units between water and commercially available weak anion exchange (WAX) and strong anion exchange (MAX) polymers, C18-modified silica, hydrophilic–lipophilic balance polymer (HLB), and Al2O3 sorbents were determined with self-packed columns using an HPLC-MS/MS setup. The anionic WAX sorbent shows a much higher adsorption affinity (about 450 fold) for PFBA than was observed for the applied hydrophobic sorbent HLB. Since the incremental value for each CF2 group is smaller when the electrostatic adsorption process is observed, the hydrophobic partition coefficient of HLB supersedes the electrostatic one of WAX at around PFTeDA. Adsorption of PFAAs to Al2O3 was weak and did not show a clear chain length dependency. A recently developed independent mode (IM) adsorption model is a more accurate model to combine the electrostatic and hydrophobic interaction terms. This model predicts the correct behaviour of especially short chain PFAAs in soil or sediment sorption experiments. Factors increasing sorption efficiency of well- and ill-defined single and multiple adsorbents towards PFAAs are discussed. The IM model provides a method to optimise sorption remediation strategies of PFAAs in contaminated waters and proposes a two step strategy, a starting hydrophobic step followed by an electrostatic one to remove more efficiently the short chain PFAAs.

Every year, hundreds of U.S. citizens patrol the Mexican border dressed in camouflage and armed with pistols and assault rifles. Unsanctioned by the government, these militias aim to stop the movement of narcotics into the United States. Recent interest in the anthropology of ethics has focused on how individuals cultivate themselves toward a notion of the ethical. In contrast, within the militias, ethical self-cultivation was absent. I argue the volunteers derived the power to be ethical from the control of the dominant moral assemblage and the construction of an immoral “Other” which provided them the power to define a moral landscape that limited the potential for ethical conflicts. In the article, I discuss two instances Border Watch and its volunteers dismissed disruptions to their moral certainty and confirmed to themselves that their actions were not only the “right” thing to do, but the only ethical response available.

Assessing the persistence of chemicals in the environment is a key element in existing regulatory frameworks to protect human health and ecosystems. Persistence in the environment depends on many fate processes, including abiotic and biotic transformations and physical partitioning, which depend on substances' physicochemical properties and environmental conditions. A main challenge in persistence assessment is that existing frameworks rely on simplistic and reductionist evaluation schemes that may lead substances to be falsely assessed as persistent or the other way around-to be falsely assessed as nonpersistent. Those evaluation schemes typically assess persistence against degradation half-lives determined in single-compartment simulation tests or against degradation levels measured in stringent screening tests. Most of the available test methods, however, do not apply to all types of substances, especially substances that are poorly soluble, complex in composition, highly sorptive, or volatile. In addition, the currently applied half-life criteria are derived mainly from a few legacy persistent organic pollutants, which do not represent the large diversity of substances entering the environment. Persistence assessment would undoubtedly benefit from the development of more flexible and holistic evaluation schemes including new concepts and methods. A weight-of-evidence (WoE) approach incorporating multiple influencing factors is needed to account for chemical fate and transformation in the whole environment so as to assess overall persistence. The present paper's aim is to begin to develop an integrated assessment framework that combines multimedia approaches to organize and interpret data using a clear WoE approach to allow for a more consistent, transparent, and thorough assessment of persistence. Integr Environ Assess Manag 2022;18:868-887. © 2021 ExxonMobil Biomedical Sciences, Inc. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental ToxicologyChemistry (SETAC).

This paper examines a biologically inspired, transforming mars rover concept known as the Transforming Roving Rolling Explorer (TRREx). The rover is designed to operate in two modes: the ‘roving’ and ‘rolling’ modes. The roving mode is similar to many traditional wheeled rover designs and is useful for exploring relatively flat terrains. The rolling mode is intended to enable the rover to travel down steep slopes, such as those found in ravines and crater walls. In the rolling mode, the vehicle folds itself into a sphere and propels itself by shifting its center of mass. It does this by opening and closing the eight panels which form the surface of the sphere. The evaluation of this rolling mode is the primary focus of this paper. To that end, a spherical prototype TRREx has been designed, constructed, and tested. In addition, a mathematical model of the vehicle’s rolling mode dynamics has been created. The performance of the physical prototype has been compared to simulation results and the qualitative agreement between the experimental and simulated results indicate that the mathematical model created for the vehicle’s rolling mode dynamics captures the essential behavior of the vehicle. The mathematical simulation was then used to explore the TRREx parameter design space in order to analyze the effect of changing various system parameters. A path tracking simulation is also included as a case study to highlight the ability of a TRREx vehicle to traverse a desired path.

Ready biodegradability tests (RBTs) are extensively used to screen the potential of chemicals to be biodegraded. The use of RBT protocols often results in large variations of test results that may lead to wrong interpretations. The present study aims to obtain a fundamental understanding of this variability. For this, we subjected the compounds 4-chloroaniline (4CA), carbamazepine (CBZ), metformin (MET), and N-methylpiperazine (NMP) to a variety of different test conditions. Inocula from five local wastewater treatment plants (WWTPs) were used in an attempt to enhance the Organisation for Economic Co-operation and Development (OECD) 310 biodegradability tests. The biodegradation capacity in RBTs, community composition and adaptation of the communities were compared after one week of pre-exposure in batch and four months exposure in chemostat. The results confirm that none of the test compounds is readily biodegradable in the standard OECD 310 RBT. However, when pre-exposure under either batch or chemostat conditions was included, 4CA was degraded in some cases and less variability among different inocula was observed for the transformation of MET. Bacterial communities from the five locations were found to be significantly different in composition from one another. In addition, pre-treatment performed before the RBT significantly changed the composition of each community. Results of this experiment show that short-term pre-exposure may increase the absolute number of degraders and deserves to be further investigated as a potential method to reduce the outcome variability of RBTs.

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 (T

We determined the degradation rates of the herbicides 2,4-D and 2,4,5-T by two different bacterial communities. One of these originated from soil heavily contaminated with herbicides from Bien Hoa airbase, the other from the same soil but amended with additional carbon and Gibbs energy sources. The community from the contaminated, but untreated, soil degraded both 2,4-D and 2,4,5-T within 5 days of cultivation. The one from the amended soil, however, hardly showed any degradation of the compounds throughout 23 days of cultivation. After refreshment of the medium and prolonged culturing, however, this community degraded both herbicides within 25 days with progressively increasing rates. nMDS analysis revealed a highly significant differentiation pattern of the two communities. Cultures inoculated with amended soil showed a significant increase of Bacillus and Paenibacillus upon prolonged exposure to the herbicides. The succession in the culture from untreated soil, on the other hand, was dominated by species from the Proteobacteria. We were able to isolate two of them and they were shown to be related to Bordetella petrii and Sphingomonas histidinilytica, successively. Subsequent PCR analyses of their DNA revealed the presence of key genes involved in the degradation of the herbicides. This study provides a more fundamental understanding of the biodegradation of 2,4-D and 2,4,5-T by displaying part of the bacterial community succession during their breakdown allowing a comprehensive view on potential key degraders.

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 (

Persistency of organic chemicals is a key property in their environmental risk assessment. Information on persistency is often derived from the results of biodegradability screening tests such as the ready biodegradability tests (RBTs). RBTs are, however, not designed for this purpose and suffer from several problems that lead to a high variability of the results and, hence, to difficulties in their interpretation. The origin and exposure history of the inocula used for biodegradability testing can lead to highly variable outcomes. Microbial adaptation to chemicals and its impact on biodegradation needs further investigation in order to have a better understanding of their effects on persistency assessments of chemicals. It is well described that microbial adaptation stimulates biodegradation of organic chemicals. Several mechanisms responsible for these phenomena have been described, amongst which are i) shifts in community composition or abundances, ii) mutations within populations, iii) horizontal gene transfer or iv) recombination events. These adaptation processes may well be mimicked under laboratory conditions, but the outcome remains difficult to predict as we lack a fundamental understanding of the adaptive responses. This review aims to bring together our current knowledge regarding microbial adaptation and its implication for the testing of biodegradation of chemicals.

A key question in microbial ecology is what the driving forces behind the persistence of large biodiversity in natural environments are. We studied a microbial community with more than 100 different types of species which evolved in a 15-years old bioreactor with benzene as the main carbon and energy source and nitrate as the electron acceptor. Using genome-centric metagenomics plus metatranscriptomics, we demonstrate that most of the community members likely feed on metabolic left-overs or on necromass while only a few of them, from families Rhodocyclaceae and Peptococcaceae, are candidates to degrade benzene. We verify with an additional succession experiment using metabolomics and metabarcoding that these few community members are the actual drivers of benzene degradation. As such, we hypothesize that high species richness is maintained and the complexity of a natural community is stabilized in a controlled environment by the interdependencies between the few benzene degraders and the rest of the community members, ultimately resulting in a food web with different trophic levels., Chrats Melkonian and colleagues use metagenomics and transcriptomics to study microbial dynamics in a 15-year old bioreactor. In contrast to what is expected in a system where benzene is the primary carbon and energy source, relatively few members of the microbial community can degrade this compound. The results have implications for understanding interdependencies within such a community.

Petroleum-industry wastewater (PI-WW) is a potential source of water that can be reused in areas suffering from water stress. This water contains various fractions that need to be removed before reuse, such as light hydrocarbons, heavy metals and conditioning chemicals. Constructed wetlands (CWs) can remove these fractions, but the range of PI-WW salinities that can be treated in CWs and the influence of an increasing salinity on the CW removal efficiency for abovementioned fractions is unknown. Therefore, the impact of an increasing salinity on the removal of conditioning chemicals benzotriazole, aromatic hydrocarbon benzoic acid, and heavy metal zinc in lab-scale unplanted and Phragmites australis and Typha latifolia planted vertical-flow CWs was tested in the present study. P. australis was less sensitive than T. latifolia to increasing salinities and survived with a NaCl concentration of 12 g/L. The decay of T. latifolia was accompanied by a decrease in the removal efficiency for benzotriazole and benzoic acid, indicating that living vegetation enhanced the removal of these chemicals. Increased salinities resulted in the leaching of zinc from the planted CWs, probably as a result of active plant defence mechanisms against salt shocks that solubilized zinc. Plant growth also resulted in substantial evapotranspiration, leading to an increased salinity of the CW treated effluent. A too high salinity limits the reuse of the CW treated water. Therefore, CW treatment should be followed by desalination technologies to obtain salinities suitable for reuse. In this technology train, CWs enhance the efficiency of physicochemical desalination technologies by removing organics that induce membrane fouling. Hence, P. australis planted CWs are a suitable option for the treatment of water with a salinity below 12 g/L before further treatment or direct reuse in water scarce areas worldwide, where CWs may also boost the local biodiversity.

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.

A key question in microbial ecology is what the driving forces behind the persistence of large biodiversity in natural environments are. We studied a microbial community with more than 100 different types of species which evolved in a 15-years old bioreactor with benzene as the main carbon and free energy source and nitrate as the electron acceptor. We demonstrate that only a few community members are able to degrade benzene, and that most of the others feed on the metabolic left-overs or on the contents of dead cells making up a food web with different trophic levels. As a result of niche partitioning, a high species richness is maintained and the complexity of a natural community is stabilized in a relatively simple environment. This view highlights the importance of species interactions and interdependencies, which drive microbial community structure and function. These mechanisms may well be conserved across ecosystems. ### Competing Interest Statement The authors have declared no competing interest.

Four bacterial strains were isolated from enrichment cultures inoculated with soil from Bien Hoa military base in Vietnam contaminated with the herbicides 2,4-dichlorophenoxyacetate (2,4-D) and 2,4,5-trichlorophenoxyacetate (2,4,5-T). They were classified as Pseudomonas aeruginosa BT1 2.2, Sphingomonas histidinilytica BT1 5.2, Bordetella petrii BT1 9.2, and Achromobacter xylosoxidans BT1 10.2, respectively. All 4 of them were able to degrade 2,4-D and 2,4,5-T during cultivation, but only the last 3 species used them as sole sources of carbon and free energy. We obtained a comprehensive insight into their degradation pathways by genomic analysis of these strains. A gene cluster with tfdCDEF genes was found in A. xylosoxidans BT1 10.2. The gene organization along with the amino acid sequences of the gene products are almost identical to those in B. petrii DSM12804. The B. petrii BT1 9.2 strain that we isolated has a full complement of the tfdABCDEF genes. Surprisingly, the gene organization along with the amino acid sequences of the gene products are virtually identical to those of Cupriavidus pinatubonensis JMP134, referred to as type I tfd genes, and clearly different from those of A. xylosoxidans and B. petrii DSM12804. Altogether, our enrichment approach has successfully resulted in boosting 3 different types of proteobacterial species that are equipped with metabolic pathways to use the herbicides as sole sources of carbon and free energy. We hypothesize that some of the corresponding genetic potential may have been recruited in recent mating events between these species and other members of the β- and γ-proteobacteria.

Biodegradable plastics made from biopolymers (made in nature) or from bio-based polymers (made in a factory) are becoming increasingly important in replacing the massive amounts of conventional, non-degradable fossil-based plastics that have been produced and disposed over the past decades. In this review we compare the biodegradation rates and mechanisms of the bioplastics thermoplastic starch, cellulose acetate and lignin based bioplastics with the biodegradation rates and mechanisms of starch, cellulose and lignin, which are the unmodified biopolymers from which these bioplastics are produced. With this comparison we aim to determine to what extent the extensive knowledge on unmodified biopolymer biodegradation can be applied to the biodegradation of bioplastics (modified biopolymers) in the terrestrial environment. This knowledge is important, since it can be of great help in giving direction to the future research and development of bioplastics and for the development of bioplastic waste assessments and policies. We found that the similarities and differences in biodegradation are dependent on the structural changes imposed on a biopolymer during the bioplastic production process. A change in higher level structure, as found in thermoplastic starch, only resulted in a limited number of differences in the biodegradation process. However, when the chemical structure of a polymer is changed, as for cellulose acetate, different microorganisms and enzymes are involved in the biodegradation. Based on the cellulose acetate biodegradation process, a conceptual model was proposed that can be used as a starting point in predicting biodegradation rates of other chemically modified biopolymers used as bioplastics. Future bioplastic biodegradation research should focus on conducting long-term field experiments, since most studies are conducted in a laboratory setting and do not capture all processes occurring in the field situation. This applies even more to lignin based bioplastics, since very little experimental data were available on modified lignin biopolymer biodegradation.

10 páginas.- 6 figuras.- 3 tablas.- 72 referencias.- The Supplemental material section includes AZ and PE molecular structures (Fig. S1) and adsorption-desorption coefficients (Tables S1 and S2). Supplementary data to this article can be found online at https://doi.org/10.1016/j.scitotenv.2019.135682, The application of biochar as a soil amendment can increase concentrations of soil organic matter, especially water-extractable organic substances. Due to their mobility and reactivity, more studies are needed to address the potential impact of biochar water-extractable substances (BWES) on the sorption of herbicides in agricultural soils that are periodically flooded. Two paddy soils (100 and 700 years of paddy soil development), unamended or amended with raw (BC) or washed biochar (BCW), were used to test the influence of BWES on the sorption behavior of the herbicides azimsulfuron (AZ) and penoxsulam (PE). The adsorption of AZ to biochar was much stronger than that to the soils, and it was adsorbed to a much larger extent to BC than to BCW. The depletion of polar groups in the BWES from the washed biochar reduced AZ adsorption but had no effect on PE adsorption. The adsorption of AZ increased when the younger soil (P100) was amended with BC and decreased when it was amended with BCW. In P700, which has lower dissolved organic carbon (DOC) content than P100, the adsorption of AZ increased regardless of whether biochar was raw or washed. The adsorption of PE slightly decreased when P100 was amended with BC or BCW and slightly increased when P700 was amended with BC or BCW. In order to evaluate compositional differences in the biochar and BWES before and after the washing treatment, we performed solid-state 13C NMR spectroscopy of BC and BCW, and high resolution mass spectrometry of BWES. Our observations stress the importance of proper consideration of soil and biochar properties before their incorporation into paddy soils, since biochar may reduce or increase the mobility of AZ and PE depending on soil properties and time of application. © 2019, This research was supported by the Ministry of Economy and Competitiveness ( AGL2016-77821-R and AGL2013-48446-C3-1-R ) and the Autonomous Government of Andalusia ( PAIDI AGR-264 ). The projects were co-financed with European funds (FEDER-FSE PO2007-13). M. García-Jaramillo thanks MEC / FECYT for a doctoral fellowship through AGL2010-21421-CO2-01 project of MICINN and for a mobility fellowship (EEBB-I-14-08137), that made possible this collaboration. This work was also in part supported by the U.S. Department of Agriculture, Agricultural Research Service ( 2072-1410-004 ).

Narratives of security and threat are continually used to justify morally contentious activities. In the past three years, the United States’ government has increasingly promoted narratives of “criminal migrants” and “immigrant invasions.” In response to perceived threats, the US-Mexico border has undergone a process of militarization. During this time, various border militias have continued to operate along the southern US border. My research was conducted over 11 months with two militias operating on the US-Mexico border I have labeled Border Watch. This militia provides a snippet of how morality is operationalized in the legitimization of actions and how morality is intrinsically linked to security in the lived experiences of its volunteers. In this article, I argue that the volunteers make sense of their experiences away from the border through the narrative espoused by the US government. The resonance between experience and narrative defines the latter as truth and the ability to dismiss counter-narratives. For the volunteers of Border Watch who adhere to a notion of citizenship through the lens of the citizen-soldier ideal, the narrative delivers a moral imperative to act in defense of the nation. Within the nexus of danger, security, and morality, the volunteers of Border Watch conceptualize their project as one in which moral citizens protect the nation and its citizens from an evil Other.

Exposure history and adaptation of the inoculum to chemicals have been shown to influence the outcome of ready biodegradability tests. However, there is a lack of information about the mechanisms involved in microbial adaptation and the implication thereof for the tests. In the present study, we investigated the impact of a long-term exposure to N-methylpiperazine (NMP) and 4-chloroaniline (4CA) of an activated sludge microbial community using chemostat systems. The objective was to characterize the influence of adaptation to the chemicals on an enhanced biodegradation testing, following the OECD 310 guideline. Cultures were used to inoculate the enhanced biodegradability tests, in batch, before and after exposure to each chemical independently in chemostat culture. Composition and diversity of the microbial communities were characterised by 16s rRNA gene amplicon sequencing. Using freshly sampled activated sludge, NMP was not degraded within the 28 d frame of the test while 4CA was completely eliminated. However, after one month of exposure, the community exposed to NMP was adapted and could completely degrade it. This result was in complete contrast with that from the culture exposed for 3 months to 4CA. Long term incubation in the chemostat system led to a progressive loss of the initial biodegradation capacity of the community, as a consequence of the loss of key degrading microorganisms. This study highlights the potential of chemostat systems to induce adaptation to a specific chemical, ultimately resulting in its biodegradation. At the same time, one should be critical of these observations as the dynamics of a microbial community are difficult to maintain in chemostat, as the loss of 4CA biodegradation capacity demonstrates.

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.

The reuse of cooling tower water (CTW) can substantially lower the freshwater footprint of cooling towers. CTW requires desalination before its reuse, and pre-treatment before desalination enhances the desalination efficiency. Constructed wetlands (CWs) have been shown to remove fractions from CTW that hamper physico-chemical desalination technologies, and thus provide adequate pre-treatment. However, CTW contains biocides, and these and their transformation products are potentially toxic to aquatic fauna in surface flow CWs. Therefore, we assessed the acute toxicity to daphnids of CTW which contained the biocide 2,2-dibromo-3-nitrilopropionamide (DBNPA), and the impact of photodegradation and the presence of biocide glutaraldehyde on its toxicity. It was observed that the toxicity of DBNPA in CTW was lower than that reported in the literature, and non-target screening showed that this was due to rapid DBNPA transformation, via 2-monobromo-3-nitrilopropionamide (MBNPA) and nitrilopropionamide (NPA). Photodegradation resulted in an increased CTW toxicity after 1 h of illumination as a result of the formation of new DBNPA transformation products, and subsequent decrease in toxicity after 48 h. The simultaneous presence of DBNPA and glutaraldehyde resulted in the formation of interaction products. Photodegradation did not result in unique interaction products, but increased the rate of interaction product formation, leading to a decrease in toxicity. Due to the toxicity of DBNPA in CTW and the effect of photodegradation on this toxicity, it is not recommended to use a surface flow CW as first treatment step in a multistage CW-system for the treatment of CTW.

The reuse of discharged cooling tower water (CTW) in the cooling tower itself could reduce fresh water intake and help mitigating fresh water scarcity problems. However, this requires desalination prior to its reuse, and hindering fractions, such as conditioning chemicals, should be removed before desalination to obtain a higher desalination efficiency. Constructed wetlands (CWs) can provide such a pre-treatment. In this study, the mechanisms underlying the removal of conditioning chemical benzotriazole (BTA) in CWs was studied using an innovative approach of differently designed pilot-scale CWs combined with batch removal experiments with substrate from these CWs. By performing these combined experiments, it was possible to determine the optimal CW design for BTA removal and the most relevant BTA removal processes in CWs. Adsorption yielded the highest contribution, and the difference in removal between different CW types was linked to their capability to aerobically biodegrade BTA. This knowledge on the main removal mechanisms for BTA allows for a CW design tailored for BTA removal. In addition, the outcomes of this research show that performing batch experiments with CW substrate allows one to determine the relevant removal mechanisms for a given compound which results in a better understanding of CW removal processes.

A significant part of our knowledge on Holocene landscape development and associated human history in northwestern Europe is based on radiocarbon dating of charcoal originating from podzols. However, these soils are characterized by leaching of soil organic matter (SOM) that may adsorb to older charcoal, resulting in incorrect charcoal radiocarbon ages. Several pretreatments, such as an acid-base-acid (ABA) sequence for Holocene-aged samples and a harsher acid-base-oxidation (ABOx) sequence for older samples, have been developed to remove the adsorbed fractions. While commonly used, evidence for the effectiveness of these pre treatments thus far has been circumstantial, by assessing the impact of these pretreatments on the radiocarbon age.In this study, we performed a direct molecular assessment of the presence, adsorption, and removal of SOM-compounds by pyrolysis-GC-MS based characterization of charcoal fragments and SOM obtained from a podzol located in the Laarder Wasmeren area, the Netherlands. In addition, the removal efficiency of adsorbed SOM by four different pretreatments was analysed. Molecular evidence for significant adsorption of SOM was found and the four pretreatments showed different efficiencies in removal thereof as evidenced by the residual charcoal composition. ABOx resulted in the most simplified Py-GC-MS chromatogram and thus comes closest to the isolation of recalcitrant carbon. The most recalcitrant organic fraction is likely to have the best interpretable age, since the highest decontamination can be expected for this fraction. Hence, it is advisable to use ABOx as standard pretreatment for the removal of adsorbed SOM fractions from charcoal, provided that the sample size is large enough.

Large volumes of freshwater are used globally for cooling towers. The reuse of discharged cooling tower water in cooling towers itself could mitigate freshwater scarcity problems. Prior to its reuse, the cooling tower blowdown has to be desalinated. However, physicochemical desalination techniques are hampered by conditioning chemicals (CC) that are added to the cooling tower water circuit to prevent corrosion, mineral scaling, and biofouling and can damage physicochemical desalination equipment. The potential of constructed wetlands (CWs) for the cost-effective removal of these CC prior to desalination is discussed in this review. The characteristics of CWs that determine their suitability for the removal of CC from cooling tower blowdown are elucidated, such as multiple removal pathways working simultaneously. In addition, specific challenges for the design of a constructed wetland for cooling tower blowdown treatment are reviewed, such as configuration options, the toxicity of CC, and the formation and removal of harmful byproducts.

A key question in microbial ecology is what the driving forces behind the persistence of large biodiversity in natural environments are. We studied a microbial community with more than 100 different types of species which evolved in a 15-years old bioreactor with benzene as the main carbon and energy source and nitrate as the electron acceptor. Using genome-centric metagenomics plus metatranscriptomics, we demonstrate that most of the community members likely feed on metabolic left-overs or on necromass while only a few of them, from families Rhodocyclaceae and Peptococcaceae, are candidates to degrade benzene. We verify with an additional succession experiment using metabolomics and metabarcoding that these few community members are the actual drivers of benzene degradation. As such, we hypothesize that high species richness is maintained and the complexity of a natural community is stabilized in a controlled environment by the interdependencies between the few benzene degraders and the rest of the community members, ultimately resulting in a food web with different trophic levels.

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.

Fullerenes are carbon based nanoparticles that may enter the environment as a consequence of both natural processes and human activities. Although little is known about the presence of these chemicals in the environment, recent studies suggested that soil may act as a sink. The aim of the present work was to investigate the presence of fullerenes in soils collected in The Netherlands. Samples (n = 91) were taken from 6 locations and analyzed using a new developed LC-QTOF-MS method. The locations included highly trafficked and industrialized as well as urban and natural areas. In general, C60 was the most abundant fullerene found in the environment, detected in almost a half of the samples and at concentrations in the range of ng/kg. Other fullerenes such as C70 and an unknown structure containing a C60 cage were detected to a lower extent. The highest concentrations were found in the proximity of combustion sites such as a coal power plant and an incinerator, suggesting that the nanoparticles were unintentionally produced during combustions processes and reached the soil through atmospheric deposition. Consistent with other recent studies, these results show that fullerenes are widely present in the environment and that the main route for their entrance may be due to human activities. These data will be helpful in the understanding of the distribution of fullerenes in the environment and for the study of their behavior and fate in soil.

The presence of certain pharmaceutical compounds in ground- and surface waters may constitute a serious environmental problem, even at low concentrations. The occurrence of pharmaceuticals in the environment indicates incomplete removal of these pharmaceuticals from municipal wastewater treatment plants (WWTPs). In this study four representative pharmaceutical compounds were identified and quantified in influent and effluent of WWTPs around the Region of Murcia. In addition, the removal efficiencies of the five different treatment systems employed by these WWTPs were evaluated for the four pharmaceutical compounds. Influent and effluent wastewaters were sampled on a weekly basis during four consecutive weeks and compound concentrations were quantitatively determined by HPLC-DAD. Pharmaceuticals were detected at μg/L levels (0.34–26.52 μg/L) in influent and effluent samples from all five different systems of the twelve WWTPs sampled in this work. The two most abundant pharmaceutical compounds were carbamazepine and naproxen. WWTPs that worked with extended aeration activated sludge processes, coagulation-flocculation, sand filtration and as tertiary treatment processes are used ultraviolet and chlorination systems (EAAS + C-F + SF + UV + Cl) removed better carbamazepine and ketoprofen than conventional activated sludge system with a double aeration tank, sand filtration, lamination, coagulation-flocculation and as tertiary treatment processes are used ultraviolet systems (CAS-DS + L + C-F + SF + UV) that removed better naproxen and diclofenac.

Brominated flame retardants account for about 21% of the total production of flame retardants and many of these have been identified as persistent, bioaccumulative and toxic. Nevertheless, debromination of these chemicals under anaerobic conditions is well established, although this can increase their toxicity. Consequently, the production and use of these chemicals has been restricted and alternative products have been developed. Many of these are brominated compounds and share some of the disadvantages of the chemicals they are meant to replace. Therefore, other, nonbrominated, flame retardants such as organophosphorus compounds are also being used in increasing quantities, despite the fact that knowledge of their biodegradation and environmental fate is often lacking.

The increasing production of fullerenes likely means a release of these chemicals in the environment. Since soils and sediments are expected to act as a sink, analytical tools are needed to assess the presence of fullerenes in these matrices. In the present work, a method was developed for the determination of fullerenes at environmental relevant levels employing Ultra High Performance Liquid Chromatograph coupled with High Resolution Mass Spectrometry (UHPLC-HRMS). Chromatographic separation was achieved with a core–shell biphenyl stationary phase that provided fast analysis with complete baseline separation. Ion Booster Electro Spray Ionization (IB-ESI) resulted in higher ionization efficiency and was much less susceptible to adduct formation in comparison with standard ESI, whereas Quadrupole Time of Flight (QTOF) MS granted high resolution mass spectra used for accurate identification. The Instrumental method limits of detection (ILoD) and quantification (ILoQ) were 6 and 20 fg, respectively, for C60 and 12 and 39 fg, respectively, for C70. Matrix effects related to co-extractants were systematically investigated in soil and sediments extracts through standard addition method (SAM) and monitoring the signal response during the chromatographic run of these samples. Consequently, minor chromatographic modifications were necessary for the analysis of matrices with high organic carbon content. The method limit of detection (MLoD)ranged from 84 pg/kg to 335 pg/kg, whereas limit of quantification (MLoQ) ranged from 279 pg/kg to 1.1 ng/kg. Furthermore, the method was successfully applied for the analysis of functionalized fullerenes (i.e. methanofullerenes). To the best of our knowledge, this is the first analytical method for the analysis of fullerenes in soils and sediments that employ core–shell biphenyl stationary phase as well as IB-ESI-QTOF MS hyphenated with UHPLC.

Microorganisms capable of degrading herbicides are essential to minimize the amount of chemical compounds that may leach into other environments. This work aimed to study the potential of sandy-loam soil fungi to tolerate the herbicide Herburon (50% diuron) and to degrade the active ingredient diuron. Verticillium sp. F04, Trichoderma virens F28, and Cunninghamella elegans B06 showed the highest growth in the presence of the herbicide. The evaluation of biotransformation showed that Aspergillus brasiliensis G08, Aspergillus sp. G25, and Cunninghamella elegans B06 had the greatest potential to degrade diuron. Statistical analysis demonstrated that glucose positively influences the potential of the microorganism to degrade diuron, indicating a cometabolic process. Due to metabolites founded by diuron biotransformation, it is indicated that the fungi are relevant in reducing the herbicide concentration in runoff, minimizing the environmental impact on surrounding ecosystems.

Venlafaxine, gemfibrozil, ibuprofen, irbesartan and ofloxacin are highly-consumed pharmaceuticals that show considerable removal efficiencies (between 40 and 98%) in wastewater treatment plants (WWTPs). Consequently, they are expected to generate transformation products (TPs) during wastewater treatment and in surface water (SW) receiving WWTP effluent. In this work, degradation experiments for these five pharmaceuticals have been carried out with SW and WWTP activated sludge under laboratory-controlled aerobic conditions to identify their transformation products by liquid chromatography coupled to time-of-flight mass spectrometry (LC-QTOF MS). Initially, 22 pharmaceutical TPs were tentatively identified. A retrospective analysis was performed in effluent wastewater (EWW) and SW samples. All parent compounds as well as several TPs were found in some of the selected EWW and SW samples. Additionally, valsartan and 3 TPs were also detected by searching for common fragments in these waters. It is important to highlight that some TPs, such as O-desmethyl-venlafaxine and an oxidized gemfibrozil TP, were more frequently found than their corresponding parent compounds. On the basis of these results, it would be recommendable to include these TPs (at least those found in EWW and SW samples analyzed) in monitoring programs in order to gain a more realistic understanding of the impact of pharmaceuticals on water quality.

The desalination and reuse of discharged cooling tower water (CTW) as feed water for the cooling tower could lower the industrial fresh water withdrawal. A potential pre-treatment method before CTW desalination is the use of constructed wetlands (CWs). Biodegradation is an important removal mechanism in CWs. In the present study, the impact of the biocides 2,2-dibromo-2-cyanoacetamide (DBNPA) and glutaraldehyde on the biodegradation process by CW microorganisms was quantified in batch experiments in which benzoic acid was incubated with realistic CTW biocide concentrations. DBNPA had a stronger negative impact on the biodegradation than glutaraldehyde. The combination of DBNPA and glutaraldehyde had a lower impact on the biodegradation than DBNPA alone. UHPLC-qTOF-MS/MS non-target screening combined with data-analysis script 'patRoon' revealed two mechanisms behind this low impact. Firstly, the presence of glutaraldehyde resulted in increased DBNPA transformation to the less toxic transformation product 2-bromo-2-cyanoacetamide (MBNPA) and newly discovered 2,2-dibromopropanediamide. Secondly, the interaction between glutaraldehyde and DBNPA resulted in the formation of new products that were less toxic than DBNPA. The environmental fate and toxicity of these products are still unknown. Nevertheless, their formation can have important implications for the simultaneous use of the biocides DBNPA and glutaraldehyde for a wide array of applications.

We investigated the occurrence of metal-based nanoparticles in a natural system, the river Dommel in the Netherlands. The river itself is well-studied as far as hydrology and water quality is concerned, easily accessible and contains one major wastewater treatment plant discharging onto this river. We sampled water from various locations along the river and collected samples of influent, effluent and sewage sludge from the wastewater treatment plant. The sampling campaign was carried out in June 2015 and these samples were analysed for seven elements using high-resolution inductively coupled plasma mass spectrometry (HR-ICP-MS), ultrafiltration with a sequence of mesh sizes and scanning electron microscopy (SEM).From the results we conclude that there are indeed nanoparticles present in the treatment plant we studied, as we found titanium and gold particles in the influent and effluent. In the river water only 10 to 20% of the mass concentration of titanium, cerium and other elements we examined is made up of free, i.e. unattached, particles with a size smaller than 20 nm or of dissolved material. The rest is attached to natural colloids or is present as individual particles or clusters of smaller particles, as it could be filtered out with 450 nm ultrafilters.We found evidence that there is no appreciable anthropogenic emission of cerium into the river, based on the geochemical relationship between cerium and lanthanum. Besides, the effluent of the treatment plant has lower concentrations of some examined elements than the surface water upstream. The treatment plant discharges much less of these elements than estimated using previous publications. However, a potential diffuse source of titanium dioxide in the form of nanoparticles or of larger particles is their use in paints and coatings, as the concentration of titanium increased considerably in the urbanised area of the river Dommel.

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.

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.

Made available in DSpace on 2018-12-11T17:35:30Z (GMT). No. of bitstreams: 0 Previous issue date: 2017-12-01 Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) The isolation of microorganisms from soil impacted by xenobiotic chemicals and exposing them in the laboratory to the contaminant can provide important information about their response to the contaminants. The purpose of this study was to isolate bacteria from soil with historical application of herbicides and to evaluate their potential to degrade diuron. The isolation media contained either glucose or diuron as carbon source. A total of 400 bacteria were isolated, with 68% being Gram-positive and 32% Gram-negative. Most isolates showed potential to degrade between 10 and 30% diuron after five days of cultivation; however Stenotrophomonas acidophila TD4.7 and Bacillus cereus TD4.31 were able to degrade 87% and 68%, respectively. The degradation of diuron resulted in the formation of the metabolites DCPMU, DCPU, DCA, 3,4-CAC, 4-CA, 4-CAC and aniline. Based on these results it was proposed that Pseudomonas aeruginosa TD2.3, Stenotrophomonas acidaminiphila TD4.7, B. cereus TD4.31 and Alcaligenes faecalis TG 4.48, act on 3,4-DCA and 4-CA by alkylation and dealkylation while Micrococcus luteus and Achromobacter sp follow dehalogenation directly to aniline. Growth on aniline as sole carbon source demonstrates the capacity of strains to open the aromatic ring. In conclusion, the results show that the role of microorganisms in the degradation of xenobiotics in the environment depends on their own metabolism and also on their synergistic interactions. Ibilce-Universidade Estadual Paulista-UNESP, São José do Rio Preto Cena-ESALQ-Universidade de São Paulo Faculty of Science Institute for Biodiversity and Ecosystem Dynamics University of Amsterdam Ibilce-Universidade Estadual Paulista-UNESP, São José do Rio Preto FAPESP: FAPESP proc 2011/50885-3R

10 páginas.-- 3 figuras.-- 70 referencias.-- Ortega Calvo, J. J. et al.., 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., All authors participated at the SETAC Europe SESSS10 symposium on bioavailability (http://sesss10.setac.eu/). They utilized of the presentations and the discussions at the symposium to write this paper. During the preparation of the symposium and this manuscript, J.-J.O.-C. was supported by the Spanish Ministry of Science and Innovation (CGL2013-44554-R). The support given by ECETOC for open access publication of this article is gratefully acknowledged.

Carbon-based nanomaterials, such as C60 fullerenes, are expected to accumulate in soil due to direct release and deposition from the atmosphere. However, little is known about the environmental fate of these nanoparticles which may be susceptible to photochemical and microbial degradation. In the present work, C60 was incubated for a period of 28 days and irradiated with UVA light. Three experiments were carried out where the fullerenes were either spiked onto a glass surface or added to quartz sand or sandy soil samples. At specific time intervals the samples were extracted and analysed by liquid chromatography coupled to UV or high resolution mass spectrometric (HRMS) detection. The fullerenes were degraded in all the treatments and the decay followed a pseudo-first-order rate law. In absence of a solid matrix, the half-life (t1⁄2) of the C60 was 13.1 days, with an overall degradation of 45.1% that was accompanied by the formation of functionalized C60-like structures. Furthermore, mass spectrometric analysis highlighted the presence of a large number of transformation products that were not directly related to the irradiation and presented opened cage and oxidized structures. When C60 was spiked into solid matrices the degradation occurred at a faster rate (t1⁄2 of 4.5 and 0.8 days for quartz sand and sandy soil, respectively). Minor but consistent losses were found in the non-irradiated samples, presumably due to biotic or chemical processes occurring in these samples. The results of this study suggest that light-mediated transformation of the fullerenes will occur in the environment.

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.

Fullerenes are carbon-based nanomaterials expected to play a major role in emerging nanotechnology and produced at an increasing rate for industrial and household applications. In the last decade a number of novel compounds (i.e. fullerene derivatives) is being introduced into the market and specific analytical methods are needed for analytical purposes as well as environmental and safety issues. In the present work eight fullerenes (C60 and C70) and functionalized fullerenes (C60 and C70 exohedral-derivatives) were selected and a novel liquid chromatographic method was developed for their analysis with UV absorption as a method of detection. The resulting HPLC-UV method is the first one suitable for the analysis of all eight compounds. This method was applied for the analysis of fullerenes added to clayish, sandy and loess top-soils at concentrations of 20, 10 and 5 μg kg(-1) and extracted with a combination of sonication and shaking extraction. The analytical method limits of detection (LoD) and limits of quantification (LoQ) were in the range of 6-10 μg L(-1) and 15-24 μg L(-1) respectively for the analytical solutions. The extraction from soil was highly reproducible with recoveries ranging from 47±5 to 71±4% whereas LoD and LoQ for all soils tested were of 3 μg kg(-1) and 10 μg kg(-1) respectively. No significant difference in the extraction performance was observed depending of the different soil matrices and between the different concentrations. The developed method can be applied for the study of the fate and toxicity of fullerenes in complex matrices at relatively low concentrations and in principle it will be suitable for the analysis of other types of functionalized fullerenes that were not included in this work.

Halogen-free flame retardants (HFFRs), such as the aromatic organophosphorus flame retardants (OPFRs) triphenyl phosphate (TPHP), resorcinol bis(diphenylphosphate) (PBDPP) and bisphenol A bis(diphenylphosphate) (BPA-BDPP) have been proposed as potential replacements for brominated flame retardants in polymers and textiles. Although these OPFRs are already marketed, their environmental fate and effects are poorly characterised. The aim of this study was therefore to determine the mineralisation and primary biodegradation of these OPFRs by activated sludge. Mineralisation was monitored by measuring CO2 production by means of GC analysis, whereas primary biodegradation was monitored by LC-MS/MS analysis of the OPFRs and their potential metabolites. TPHP was biodegraded and mineralised most rapidly and achieved the requirement for ready biodegradability (60% of theoretical maximum mineralisation). Primary biodegradation was also rapid for PBDPP, but 60% mineralisation was not achieved within the time of the test, suggesting that transformation products of PBDPP may accumulate. Primary degradation of BPA-BDPP was very slow and very low CO2 production was also observed. Based on these results, TPHP and to a lesser extent PBDPP appear to be suitable replacements for the more environmentally persistent brominated flame retardants.