RESUMO
Bioaccumulation of persistent and hydrophobic organic compounds in the aquatic environment puts secondary consumers, such as fish, at risk. To assess their exposure, monitoring programs with high numbers of individuals have been conducted worldwide over decades that require major efforts and raise ethical issues. This study aimed at testing suspended particulate matter (SPM) as an alternative and accessible abiotic matrix to estimate the internal exposure concentrations of such chemicals in fish and mussels. Muscle tissues of bream (Abramis brama), tissues of zebra mussels (Dreissena polymorpha) and SPM were collected from four major German rivers, Elbe, Danube, Saar and Saale, in 2018 within the national monitoring program of the German Environmental Specimen Bank. We used (i) total solvent extraction for biota samples to quantify the lipid-normalized concentrations of polychlorinated biphenyls, polycyclic aromatic hydrocarbons and hexachlorobenzene and (ii) passive equilibrium sampling of SPM to derive equilibrium partitioning concentrations in lipids and (iii) set these independent data sets into context. Since the ratio of lipid-normalized concentration / equilibrium partitioning concentration in lipids was in most cases <â¯1.0, SPM may serve as a conservative proxy for the internal concentration of bream and mussels, although bream of high age (i.e., older than 10 years) showed a tendency for this ratio to exceed 1.0. This observation indicates that age-dependent biomagnification can exceed the predictions based on thermodynamic equilibrium relative to SPM.
Assuntos
Bivalves , Poluentes Químicos da Água , Animais , Monitoramento Ambiental , Material Particulado/análise , Rios/química , Poluentes Químicos da Água/análiseRESUMO
Applying activated carbon (AC) to contaminated sediments is an in-situ approach to remediation with great potential. The bioavailability of persistent organic pollutants can be rapidly reduced and kept low over long periods of time. However, there are limitations to the method. The high buoyancy of AC particles makes their application difficult in the field, and AC retention on the amended site can be low in turbulent waters. Furthermore, the fine particles of powdered AC (PAC) can have adverse effects on organisms, but their remediation potential is superior to coarser, granular ACs (GAC). To tackle these shortcomings, a novel sorbent material was developed, consisting of PAC embedded into a stable, granular clay-matrix, significantly reducing buoyancy. These AC-clay granules (ACC-G) were tested for remediation potential (PCB-bioaccumulation reduction) and adverse effects on the benthic invertebrates Chironomus riparius and Lumbriculus variegatus. The novel ACC-G material was compared to GAC of the same particle size, the clay-matrix, and PAC. The findings show that ACC-G has a significantly higher remediation potential than GAC, allowing for reductions in PCB-bioaccumulation of up to 89%. Adverse effects could not be totally eliminated with ACC-G, but they were less severe than with PAC, likely due to the increased particle size.
Assuntos
Chironomidae , Poluentes Ambientais , Recuperação e Remediação Ambiental , Oligoquetos , Poluentes Químicos da Água , Animais , Carvão Vegetal , Sedimentos GeológicosRESUMO
Whereas specially designed dinitroxide biradicals, reconstitution protocols, oriented sample geometries and NMR probes have helped to much increase the DNP enhancement factors of membrane samples they still lag considerably behind those obtained from glasses made of protein solutions. Here we show that not only the MAS rotor material but also the distribution of the membrane samples within the NMR rotor have a pronounced effect on the DNP enhancement. These observations are rationalized with the cooling efficiency and the internal properties of the sample, monitored by their T1 relaxation, microwave ON versus OFF signal intensities and DNP effect. The data are suggestive that for membranes the speed of cooling has a pronounced effect on the membrane properties and concomitantly the distribution of biradicals within the sample.
RESUMO
The in situ remediation of aquatic sediments with activated carbon (AC)-based thin layer capping is a promising alternative to traditional methods, such as sediment dredging. Applying a strong sorbent like AC directly to the sediment can greatly reduce the bioavailability of organic pollutants. To evaluate the method under realistic field conditions, a 300 m2 plot in the PCB-contaminated Lake Kernaalanjärvi, Finland, was amended with an AC cap (1.6 kgAC/m2). The study lake showed highly dynamic sediment movements over the monitoring period of 14 months. This led to poor retention and rapid burial of the AC cap under a layer of contaminated sediment from adjacent sites. As a result, the measured impact of the AC amendment was low: Both the benthic community structure and PCB bioaccumulation were similar on the plot and in surrounding reference sites. Corresponding follow-up laboratory studies using Lumbriculus variegatus and Chironomus riparius showed that long-term remediation success is possible, even when an AC cap is covered with contaminated sediment. To retain a measurable effectiveness (reduction in contaminant bioaccumulation), a sufficient intensity and depth of bioturbation is required. On the other hand, the magnitude of the adverse effect induced by AC correlated positively with the measured remediation success.
Assuntos
Chironomidae , Poluentes Químicos da Água , Animais , Carvão Vegetal , Finlândia , Sedimentos Geológicos , LagosRESUMO
BACKGROUND: In situ sorbent amendment for persistent organic pollutant sequestration in sediment has over the past 15 years steadily progressed from bench-scale trials to full-scale remediation applications. Hindering a wider technology uptake are, however, concerns about ecotoxic side-effects of the most commonly used sorbent, activated carbon, on sensitive, sediment dwelling organisms like Lumbriculus variegatus. Using River Tyne sediment polluted with polycyclic aromatic hydrocarbons (PAHs) and L. variegatus as a case study, sorbent alternatives and magnetic sorbent-recovery were investigated as potential engineering strategies to mitigate such ecotoxic side-effects. The potential benefits of contacting the treated sediment with fresh River Tyne water, as would naturally occur over time in the intended applications, were studied. RESULTS: Magnetic biochar was identified as an effective PAH sorbent with less ecotoxic side-effects than magnetic activated carbon. After 85.1-100% magnetic recovery of this biochar, no ecotoxic side-effects on L. variegatus were measurable in the treated sediment. Results show that ecotoxic effects of magnetic activated carbon can be alleviated through sorbent recovery. In contrast, contacting treated sediment repeatedly with River Tyne water had no measurable benefits. CONCLUSIONS: Magnetic biochar is a promising sorbent material for the remediation of PAH polluted sediment. © 2017 The Authors. Journal of Chemical Technology & Biotechnology published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.
RESUMO
The nonbiting midge Chironomus riparius was used to study the remediation potential and secondary effects of activated carbon (AC, ø 63-200 µm) in PCB contaminated sediments. AC amendments efficiently reduced PCB bioavailability determined by Chironomus riparius bioaccumulation tests and passive samplers. PCBs were shown to transfer from larvae to adults. Lower PCB concentrations were observed in adult midges emerging from AC amended compared to unamended sediments. Increased reproduction, survival, larval growth and gut wall microvilli length were observed with low AC dose (0.5% sediment dw) compared to unamended sediment, indicating an improved success of larvae in the sediment with low organic carbon content. On the other hand, higher AC doses (2.5% sediment dw) caused adverse effects on emergence and larval development. In addition, morphological changes in the gut wall microvilli layer were observed. This study showed that the secondary effects of AC amendments are dependent on the dose and the sediment characteristics. Metamorphic species, such as C. riparius, may act as a vector for organic pollutants from aquatic to terrestrial ecosystems and according to this study the AC amendments may reduce this transport.
Assuntos
Chironomidae/efeitos dos fármacos , Sedimentos Geológicos , Animais , Carbono/farmacologia , Carvão Vegetal/farmacologia , Bifenilos PolicloradosRESUMO
Persistent organic pollutants (POPs) pose a risk in aquatic environments. In sediment, this risk is frequently evaluated using total or organic carbon-normalized concentrations. However, complex physicochemical sediment characteristics affect POP bioavailability in sediment, making its prediction a challenging task. This task can be addressed using chemical activity, which describes a compound's environmentally effective concentration and can generally be approximated by the degree of saturation for each POP in its matrix. We present a proof of concept to load artificial sediments with POPs to reach a target chemical activity. This approach is envisioned to make laboratory ecotoxicological bioassays more reproducible and reduce the impact of sediment characteristics on the risk assessment. The approach uses a constantly replenished, saturated, aqueous POP solution to equilibrate the organic carbon fraction (e.g., peat) of an artificial sediment, which can be further adjusted to target chemical activities by mixing with clean peat. We demonstrate the applicability of this approach using four polycyclic aromatic hydrocarbons (acenaphthene, fluorene, phenanthrene, and fluoranthene). Within 5 to 17 weeks, the peat slurry reached a chemical equilibrium with the saturated loading solution. We used two different peat batches (subsamples from the same source) to evaluate the approach. Variations in loading kinetics and eventual equilibrium concentrations were evident between the batches, which highlights the impact of even minor disparities in organic carbon properties within two samples of peat originating from the same source. This finding underlines the importance of moving away from sediment risk assessments based on total concentrations. The value of the chemical activity-based loading approach lies in its ability to anticipate similar environmental impacts, even with varying contaminant concentrations. Environ Toxicol Chem 2024;43:279-287. © 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.
Assuntos
Poluentes Ambientais , Hidrocarbonetos Policíclicos Aromáticos , Poluentes Químicos da Água , Monitoramento Ambiental , Sedimentos Geológicos/química , Poluentes Químicos da Água/análise , Hidrocarbonetos Policíclicos Aromáticos/análise , Bioensaio , Carbono , SoloRESUMO
As a large group of chemicals with diverse properties, per- and polyfluoroalkyl substances (PFAS) have found extensive application throughout consumer products, including cosmetics. Little is known about the importance of dermal uptake as a human exposure pathway for PFAS. Here we investigate a suite of listed-ingredient and residual PFAS in cosmetic products, along with their dermal bioaccessibility using in vitro incubations with artificial sweat. Concentrations of volatile listed ingredients (including cyclic perfluorinated alkanes, perfluorinated ethers, and polyfluorinated silanes) in three products ranged from 876-1323 µg g-1, while polar listed ingredients (i.e., polyfluoroalkyl phosphate esters [PAPs]) in a single product occurred at up to 2427 µg g-1 (6 : 2/6 : 2 diPAP)). Residual perfluoroalkyl carboxylic acids (PFCAs) were also measured at concentrations ranging from 0.02-29 µg g-1. When listed ingredients were included, our targeted analysis accounted for up to 103% of the total fluorine, while highlighting ambiguous and/or incorrect International Nomenclature of Cosmetic Ingredient (INCI) names used in several products. Bioaccessibility experiments revealed that residual PFCAs readily partitioned to artificial sweat (bioaccessible fractions ranging from 43-76% for detectable substances) while listed ingredients (i.e., PAPs and neutral/volatile PFAS) displayed negligible partitioning. This work provides new insight into the occurrence of PFAS in cosmetic products, while furthering our understanding on their mechanisms of dermal uptake.
Assuntos
Cosméticos , Fluorocarbonos , Humanos , Ácidos Carboxílicos , Fluorocarbonos/análiseRESUMO
The production and release of chemicals from human activities are on the rise. Understanding how the aquatic environment is affected by the presence of an unknown number of chemicals is lacking. We employed the chemical activity concept to assess the combined effects of hydrophobic organic contaminants on the phytoplankton species Rodomonas salina. Chemical activity is additive, and refers to the relative saturation of a chemical in the studied matrix. The growth of R. salina was affected by chemical activity, following a chemical activity-response curve, resulting in an Ea50 value of 0.078, which falls within the baseline toxicity range observed in earlier studies. The chlorophyll a content exhibited both increases and decreases with rising chemical activity, with the increase possibly linked to an antioxidant mechanism. Yet, growth inhibition provided more sensitive and robust responses compared to photosynthesis-related endpoints; all measured endpoints correlated with increased chemical activity. Growth inhibition is an ecologically relevant endpoint and integrates thermodynamic principles such as membrane disruption. Our study utilized passive dosing, enabling us to control exposure and determine activities in both the medium and the algae. The concept of chemical activity and our results can be extended to other neutral chemical groups as effects of chemical activity remain independent of the mixture composition.
Assuntos
Artrópodes , Poluentes Químicos da Água , Animais , Humanos , Clorofila A , Poluentes Químicos da Água/toxicidade , Interações Hidrofóbicas e Hidrofílicas , FitoplânctonRESUMO
Burial of persistent organic pollutants (POPs) such as polychlorinated biphenyls (PCBs) in deep-sea sediments contributes to 60% of their historical emissions. Yet, empirical data on their occurrence in the deep-ocean is scarce. Estimates of the deep-ocean POP sink are therefore uncertain. Hadal trenches, representing the deepest part of the ocean, are hotspots for organic carbon burial and decomposition. POPs favorably partition to organic carbon, making trenches likely significant sinks for contaminants. Here we show that PCBs occur in both hadal (7720-8085 m) and non-hadal (2560-4050 m) sediment in the Atacama Trench. PCB concentrations normalized to sediment dry weight were similar across sites while those normalized to sediment organic carbon increased exponentially as the inert organic carbon fraction of the sediment increased in degraded hadal sediments. We suggest that the unique deposition dynamics and elevated turnover of organic carbon in hadal trenches increase POP concentrations in the deepest places on Earth.
RESUMO
There are several methods for studying metal-contaminated freshwater sediments, but more information is needed on which methods to include in ecological risk assessment. In this study, we compliment the traditional Sediment Quality Triad (SQT) approach - including information on chemistry, toxicity and ecological status - with studies on metal bioavailability and metal body residues in local organisms. We studied four mining-affected boreal lakes in Finland by conducting chemical analyses of sediment and water, toxicity tests (L. variegatus, V. fischeri, C. riparius, L. stagnalis), and analysis of benthic organism community structure. In addition, we studied the relationships between metal loading, toxicity, metal bioavailability, and metal body residues in the field-collected biota. Chemistry and benthic organism community structures show adverse effects in those lakes, where the metal concentrations are the highest. However, toxicity was connected to low sediment pH during the experiment, rather than to high metal concentrations. Toxicity was observed in 4 out of 6 toxicity tests including growth test with L. variegatus, bulk sediment test with V. fischeri, and the L. stagnalis toxicity test. The C. riparius test did not show toxicity. Metal body residues in biota were not high enough to induce adverse effects (0.1-4.1â¯mgâ¯Cu/kg fw, 0.01-0.3â¯mgâ¯Ni/kg fw, 2.9-26.7â¯mgâ¯Zn/kg fw and 0.01-0.7â¯mgâ¯As/kg fw). Chemical analyses, metal bioavailability assessment and benthic community structures survey revealed adverse effects in the sediments, where metal concentrations are highest (Lake SJ and Lake KS). Standard toxicity tests were not suitable for studying acid, sulfide-rich sediments and, therefore, benthic structure study and chemical analyses are believed to give more reliable results of the ecological status of these sediments.
Assuntos
Peixes/metabolismo , Sedimentos Geológicos/análise , Invertebrados/efeitos dos fármacos , Lagos/análise , Metais/toxicidade , Vibrio/efeitos dos fármacos , Poluentes Químicos da Água/toxicidade , Animais , Disponibilidade Biológica , Finlândia , Mineração , Medição de Risco , Testes de ToxicidadeRESUMO
Activated carbon (AC) has been proven to be highly effective for the in-situ remediation of sediments contaminated with a wide range of hydrophobic organic contaminants (HOCs). However, adverse biological effects, especially to benthic organisms, can accompany this promising remediation potential. In this study, we compare both the remediation potential and the biological effects of several AC materials for two application methods: mixing with sediment (MIX) at doses of 0.1 and 1.0% based on sediment dw and thin layer capping (TLC) with 0.6 and 1.2 kg AC/m2. Significant dose dependent reductions in PCB bioaccumulation in Lumbriculus variegatus of 35-93% in MIX treatments were observed. Contaminant uptake in TLC treatments was reduced by up to 78% and differences between the two applied doses were small. Correspondingly, significant adverse effects were observed for L. variegatus whenever AC was present in the sediment. The lowest application dose of 0.1% AC in the MIX system reduced L. variegatus growth, and 1.0% AC led to a net loss of organism biomass. All TLC treatments let to a loss of biomass in the test organism. Furthermore, mortality was observed with 1.2 kg AC/m2 doses of pure AC for the TLC treatment. The addition of clay (Kaolinite) to the TLC treatments prevented mortality, but did not decrease the loss in biomass. While TLC treatments pose a less laborious alternative for AC amendments in the field, the results of this study show that it has lower remediation potential and could be more harmful to the benthic fauna.
Assuntos
Carvão Vegetal/química , Sedimentos Geológicos/química , Animais , Oligoquetos/efeitos dos fármacosRESUMO
The biological effects of activated carbon (AC) amendments in sediments were studied with the midge Chironomus riparius. The effects on larvae growth were studied using three different AC particles sizes (PAC: 90% <63µm, MAC: ø 63-200µm and GAC: ø 420-1700µm). The long- term effects of MAC were studied in an emergence experiment over two generations (P, F1), together with larvae growth experiment over three generations (P, F1, F2). Retarded growth and development of the larvae were observed in the two smallest particle sizes (PAC and MAC), as well as morphological changes in the gut wall microvilli layer studied from transmission electron micrographs. In addition, at high AC treatments the larvae reaching fourth instar stage were of a smaller size compared to the controls. With PAC treatment AC amendment dosages higher than 1% of sediment dry weight induced mortality. In the emergence experiment there was an indication of a delay in F1 generation emergence. Male dry weight (dw) in P generation was significantly reduced in the 2.5% MAC treatment. The effects of AC amendments were more obvious in the C. riparius larvae compared to the effects seen in emerging adults exposed to AC-amended sediment during the larval stage.
Assuntos
Carvão Vegetal/química , Chironomidae/metabolismo , Sedimentos Geológicos/química , Animais , Carvão Vegetal/toxicidade , Chironomidae/efeitos dos fármacos , Chironomidae/crescimento & desenvolvimento , Crescimento/efeitos dos fármacos , Larva/efeitos dos fármacos , Larva/crescimento & desenvolvimento , Tamanho da Partícula , Reprodução/efeitos dos fármacos , Razão de Masculinidade , Análise de Sobrevida , Água/análise , Poluentes Químicos da ÁguaRESUMO
Addition of activated carbon (AC) or biochar (BC) to sediment to reduce the chemical and biological availability of organic contaminants is a promising in-situ remediation technology. But concerns about leaving the adsorbed pollutants in place motivate research into sorbent recovery methods. This study explores the use of magnetic sorbents. A coal-based magnetic activated carbon (MAC) was identified as the strongest of four AC and BC derived magnetic sorbents for polycyclic aromatic hydrocarbons (PAHs) remediation. An 8.1% MAC amendment (w/w, equal to 5% AC content) was found to be as effective as 5% (w/w) pristine AC in reducing aqueous PAHs within three months by 98%. MAC recovery from sediment after three months was 77%, and incomplete MAC recovery had both, positive and negative effects. A slight rebound of aqueous PAH concentrations was observed following the MAC recovery, but aqueous PAH concentrations then dropped again after six months, likely due to the presence of the 23% unrecovered MAC. On the other hand, the 77% recovery of the 8.1% MAC dose was insufficient to reduce ecotoxic effects of fine grained AC or MAC amendment on the egestion rate, growth and reproduction of the AC sensitive species Lumbriculus variegatus.
Assuntos
Carbono/química , Recuperação e Remediação Ambiental/métodos , Hidrocarbonetos Policíclicos Aromáticos/química , Purificação da Água/métodos , Animais , Carvão Vegetal/química , Carvão Mineral , Ecologia , Sedimentos Geológicos , Cinética , Magnetismo , Microscopia Eletrônica de Varredura , Oligoquetos/efeitos dos fármacos , Tamanho da Partícula , Reprodutibilidade dos Testes , Água/química , Poluentes da Água/química , Poluentes Químicos da Água/análiseRESUMO
La evaluaciòn del riesgo cardiovascular preoperatorio en la cirugìa no cardìaca es una consulta frecuente en la pràctica diaria y las complicaciones cardìovasculares son una de las principales causas de morbimortalidad en el posoperatorio..