Biomass integrated gasification combined cycle (IGCC) is attracting increased interest because it can achieve high system energy efficiency (>50%), which is predicted to increase with the increase in the solar share in biomass IGCC. This study evaluated the potential of crop residues numerically for the co-production of power and bio-fertilizer using ASPEN Plus® simulation software. The results showed that the gas yield increases with increasing temperature and decreasing pressure while the yield of bio-fertilizer is dependent on the biomass composition. The biomass with a low ash content produces high bio-fertilizer at the designated gasification temperature. The IGCC configuration conserves more energy than a directly-fired biomass power plant. In addition, the solar-assisted IGCC attains a higher net electricity output per unit of crop residue feed and achieves net thermal efficiencies of around 53%. The use of such hybrid systems offer the potential to produce 0.55 MW of electricity per unit of solar-thermal energy at a relatively low cost. The ASPEN Plus model predicted that the solar biomass-based IGCC set up is more efficient in increasing the power generation capacity than any other conversion system. The results showed that a solar to electricity efficiency of approximately 55% is achievable with potential improvements. This work will contribute for the sustainable bioenergy production as the relationship between energy production and biomass supplies very important to ensure the food security and environmental sustainability.

The oxidation of magnetite into maghemite and its coating by natural organic constituents are common changes that affect the reactivity of iron oxide nanoparticles (IONP) in aqueous environments. Certain ubiquitous compounds such as humic acids (HA) and phosphatidylcholine (PC), displaying a high affinity for both copper (Cu) and IONP, could play a critical role in the interactions involved between both compounds. The adsorption of Cu onto four different IONP was studied: magnetite nanoparticles (magnNP), maghemite NP (maghNP), HA- and PC-coated magnetite NP (HA-magnNP and PC-magnNP, respectively). According to the results, the percentage of adsorbed Cu increases with increasing pH, irrespective of the IONP. Thus, protonation/deprotonation reactions are likely involved within Cu adsorption mechanism. Contrary to the other studied IONP, HA-magnNP favor Cu adsorption at most of the pH tested including acidic pH (pH = 3), suggesting that part of the active surface sites for Cu²⁺ were not grabbed by protons. The Freundlich adsorption isotherm of HA-magnNP provides the highest sorption constant KF (bonding energy) and n value which supports a heterogeneous sorption process. The heterogeneous adsorption between HA-magnNP and Cu²⁺ can be explained by both the diversity of the binding sites HA procured and the formation of multidendate complexes between Cu²⁺ and some of the HA functional groups. Such favorable adsorption process was neither observed on PC-coated-magnNP nor on maghNP, whose behaviors were comparable to that of magnNP. On another hand, HA and PC coatings considerably reduced iron (Fe) dissolution from magnNP as compared with magnNP. It was suggested that HA and PC coatings either provided efficient shield against Fe leaching or fostered dissolved Fe re-adsorption onto the functional groups at the coated magnNP surfaces. Thus, this study can help to better understand the complex interfacial reactions between cations-organic matter-colloidal surfaces which are relevant in environmental and agricultural contexts.This work showed that magnetite NP properties can be affected by surface modifications, which drive NP chemical stability and Cu adsorption, thereby affecting the global water chemistry.

International audience | The oxidation of magnetite into maghemite and its coating by natural organic constituents are common changes that affect the reactivity of iron oxide nanoparticles (IONP) in aqueous environments. Certain ubiquitous compounds such as humic acids (HA) and phosphatidylcholine (PC), displaying a high affinity for both copper (Cu) and IONP, could play a critical role in the interactions involved between both compounds. The adsorption of Cu onto four different IONP was studied: magnetite nanoparticles (magnNP), maghemite NP (maghNP), HA- and PC-coated magnetite NP (HA-magnNP and PC-magnNP, respectively). According to the results, the percentage of adsorbed Cu increases with increasing pH, irrespective of the IONP. Thus, protonation/deprotonation reactions are likely involved within Cu adsorption mechanism. Contrary to the other studied IONP, HA-magnNP favor Cu adsorption at most of the pH tested including acidic pH (pH = 3), suggesting that part of the active surface sites for Cu2+ were not grabbed by protons. The Freundlich adsorption isotherm of HA-magnNP provides the highest sorption constant KF (bonding energy) and n value which supports a heterogeneous sorption process. The heterogeneous adsorption between HA-magnNP and Cu2+ can be explained by both the diversity of the binding sites HA procured and the formation of multidendate complexes between Cu2+ and some of the HA functional groups. Such favorable adsorption process was neither observed on PC-coated-magnNP nor on maghNP, whose behaviors were comparable to that of magnNP. On another hand, HA and PC coatings considerably reduced iron (Fe) dissolution from magnNP as compared with magnNP. It was suggested that HA and PC coatings either provided efficient shield against Fe leaching or fostered dissolved Fe re-adsorption onto the functional groups at the coated magnNP surfaces. Thus, this study can help to better understand the complex interfacial reactions between cations-organic matter-colloidal surfaces which are relevant in environmental and agricultural contexts.This work showed that magnetite NP properties can be affected by surface modifications, which drive NP chemical stability and Cu adsorption, thereby affecting the global water chemistry.

Despite the ubiquitous and persistent presence of microplastic (MP) in marine ecosystems, knowledge of its potential harmful ecological effects is low. In this work, we assessed the risk of floating MP (1 μm–5 mm) to marine ecosystems by comparing ambient concentrations in the global ocean with available ecotoxicity data. The integration of twenty-three species-specific effect threshold concentration data in a species sensitivity distribution yielded a median unacceptable level of 1.21 ∗ 10⁵ MP m⁻³ (95% CI: 7.99 ∗ 10³–1.49 ∗ 10⁶ MP m⁻³). We found that in 2010 for 0.17% of the surface layer (0–5 m) of the global ocean a threatening risk would occur. By 2050 and 2100, this fraction increases to 0.52% and 1.62%, respectively, according to the worst-case predicted future plastic discharge into the ocean. Our results reveal a spatial and multidecadal variability of MP-related risk at the global ocean surface. For example, we have identified the Mediterranean Sea and the Yellow Sea as hotspots of marine microplastic risks already now and even more pronounced in future decades.

Despite the ubiquitous and persistent presence of microplastic (MP) in marine ecosystems, knowledge of its potential harmful ecological effects is low. In this work, we assessed the risk of floating MP (1 μm – 5 mm) to marine ecosystems by comparing ambient concentrations in the global ocean with available ecotoxicity data. The integration of twenty-three species-specific effect threshold concentration data in a species sensitivity distribution yielded a median unacceptable level of 1.21 * 105 MP m-³ (95% CI: 7.99 * 103 – 1.49 * 106 MP m-³). We found that in 2010 for 0.17% of the surface layer (0 – 5 m) of the global ocean a threatening risk would occur. By 2050 and 2100, this fraction increases to 0.52% and 1.62%, respectively, according to the worst-case predicted future plastic discharge into the ocean. Our results reveal a spatial and multidecadal variability of MP-related risk at the global ocean surface. For example, we have identified the Mediterranean Sea and the Yellow Sea as hotspots of marine microplastic risks already now and even more pronounced in future decades.

Pharmaceuticals such as non-steroidal anti-inflammatory drugs (NSAIDs) have been found in the marine environment. Although there is a large body of evidence that pharmaceutical drugs exert negative impacts on aquatic organisms, especially in the freshwater compartment, only limited studies are available on bioconcentration and the effects of NSAIDs on marine organisms. Bivalves have a high ecological and socio-economic value and are considered good bioindicator species in ecotoxicology and risk assessment programs. Therefore, this review summarizes current knowledge on the bioconcentration and the effects of three widely used NSAIDs, diclofenac, ibuprofen and paracetamol, in marine bivalves exposed under laboratory conditions. These pharmaceutical drugs were chosen based on their environmental occurrence both in frequency and concentration that may warrant their inclusion in the European Union Watch List. It has been highlighted that ambient concentrations may result in negative effects on wild bivalves after long-term exposures. Also, higher trophic level organisms may be more impacted due to food-chain transfer (e.g., humans are shellfish consumers). Overall, the three selected NSAIDs were reported to bioconcentrate in marine bivalves, with recognized effects at different life-stages. Immune responses were the main target of a long-term exposure to the drugs. The studies selected support the inclusion of diclofenac on the European Union Watch List and highlight the importance of extending research for ibuprofen and paracetamol due to their demonstrated negative effects on marine bivalves exposed to environmental realistic concentrations, under laboratory conditions.

11 pages, 1 figure, 2 tables | Pharmaceuticals such as non-steroidal anti-inflammatory drugs (NSAIDs) have been found in the marine environment. Although there is a large body of evidence that pharmaceutical drugs exert negative impacts on aquatic organisms, especially in the freshwater compartment, only limited studies are available on bioconcentration and the effects of NSAIDs on marine organisms. Bivalves have a high ecological and socio-economic value and are considered good bioindicator species in ecotoxicology and risk assessment programs. Therefore, this review summarizes current knowledge on the bioconcentration and the effects of three widely used NSAIDs, diclofenac, ibuprofen and paracetamol, in marine bivalves exposed under laboratory conditions. These pharmaceutical drugs were chosen based on their environmental occurrence both in frequency and concentration that may warrant their inclusion in the European Union Watch List. It has been highlighted that ambient concentrations may result in negative effects on wild bivalves after long-term exposures. Also, higher trophic level organisms may be more impacted due to food-chain transfer (e.g., humans are shellfish consumers). Overall, the three selected NSAIDs were reported to bioconcentrate in marine bivalves, with recognized effects at different life-stages. Immune responses were the main target of a long-term exposure to the drugs. The studies selected support the inclusion of diclofenac on the European Union Watch List and highlight the importance of extending research for ibuprofen and paracetamol due to their demonstrated negative effects on marine bivalves exposed to environmental realistic concentrations, under laboratory conditions | Ângela Almeida benefited from PhD grant (SFRH/BD/110218/2015) given by the National Funds through the Portuguese Science Foundation (FCT), supported by FSE and Programa Operacional Capital Humano (POCH) e European Union. Rosa Freitas was funded by national funds (OE), through FCT – Fundação para a Ciência e a Tecnologia, I.P., in the scope of the framework contract foreseen in the numbers 4, 5 and 6 of the article 23, of the Decree-Law 57/2016, of August 29, changed by Law 57/2017, of July 19. This work was also financially supported by the project BISPECIAl: BIvalveS under Polluted Environment and ClImate chAnge PTDC/CTA-AMB/28425/2017 (POCI-01-0145-FEDER-028425) funded by FEDER, through COMPETE2020 - Programa Operacional Competitividade e Internacionalização (POCI), and by national funds (OE), through FCT/MCTES. Thanks are due for the financial support to CESAM (UIDB/50017/2020+UIDP/50017/2020), to FCT/MEC through national funds, and the co-funding by the FEDER, within the PT2020 Partnership Agreement and Compete 2020. The authors also acknowledge to the RED RIESCOS - Evaluación de los Efectos de los Contaminantes Emergentes en Organismos Acuáticos y sobre la Salud Humana, from the Programa Iberoamericano de Ciencia y Tecnología para el Desarrollo (CYTED) with the reference 419RT0578 | With the funding support of the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000928-S), of the Spanish Research Agency (AEI)

Pharmaceuticals such as non-steroidal anti-inflammatory drugs (NSAIDs) have been found in the marine environment. Although there is a large body of evidence that pharmaceutical drugs exert negative impacts on aquatic organisms, especially in the freshwater compartment, only limited studies are available on bioconcentration and the effects of NSAIDs on marine organisms. Bivalves have a high ecological and socio-economic value and are considered good bioindicator species in ecotoxicology and risk assessment programs. Therefore, this review summarizes current knowledge on the bioconcentration and the effects of three widely used NSAIDs, diclofenac, ibuprofen and paracetamol, in marine bivalves exposed under laboratory conditions. These pharmaceutical drugs were chosen based on their environmental occurrence both in frequency and concentration that may warrant their inclusion in the European Union Watch List. It has been highlighted that ambient concentrations may result in negative effects on wild bivalves after long-term exposures. Also, higher trophic level organisms may be more impacted due to food-chain transfer (e.g., humans are shellfish consumers). Overall, the three selected NSAIDs were reported to bioconcentrate in marine bivalves, with recognized effects at different life-stages. Immune responses were the main target of a long-term exposure to the drugs. The studies selected support the inclusion of diclofenac on the European Union Watch List and highlight the importance of extending research for ibuprofen and paracetamol due to their demonstrated negative effects on marine bivalves exposed to environmental realistic concentrations, under laboratory conditions. | published

Organic chemical pollutants associated with microplastic (MP) may represent an alternative exposure route for these chemicals to marine biota. However, the bioavailability of MP-sorbed organic pollutants under conditions where co-exposure occurs from the same compounds dissolved in the water phase has rarely been studied experimentally, especially where pollutant concentrations in the two phases are well characterized. Importantly, higher concentrations of organic pollutants on ingested MP may be less bioavailable to aquatic organisms than the same chemicals present in dissolved form in the surrounding water. In the current study, the sorption kinetics of two model polycyclic aromatic hydrocarbons (PAHs; fluoranthene and phenanthrene) to MP particles in natural seawater at 10 and 20 °C were studied and the bioavailability of MP-sorbed PAHs to marine copepods investigated. Polyethylene (PE) and polystyrene (PS) microbeads with mean diameters ranging from 10 to 200 μm were used to identify the role of MP polymer type and size on sorption mechanisms. Additionally, temperature dependence of sorption was investigated. Results indicated that adsorption dominated at lower temperatures and for smaller MP (10 μm), while absorption was the prevailing process for larger MP (100 μm). Monolayer sorption dominated at lower PAH concentrations, while multilayer sorption dominated at higher concentrations. PE particles representing ingestible (10 μm) and non-ingestible (100 μm) MP for the marine copepod species Acartia tonsa and Calanus finmarchicus were used to investigate the availability and toxicity of MP-sorbed PAHs. Studies were conducted under co-exposure conditions where the PAHs were also present in the dissolved phase (Cfᵣₑₑ), thereby representing more environmentally relevant exposure scenarios. Cfᵣₑₑ reduction through MP sorption was reflected in a corresponding reduction of lethality and bioaccumulation, with no difference observed between ingestible and non-ingestible MP. This indicates that only free dissolved PAHs are significantly bioavailable to copepods under co-exposure conditions with MP-sorbed PAHs.

Organic chemical pollutants associated with microplastic (MP) may represent an alternative exposure route for these chemicals to marine biota. However, the bioavailability of MP-sorbed organic pollutants under conditions where co-exposure occurs from the same compounds dissolved in the water phase has rarely been studied experimentally, especially where pollutant concentrations in the two phases are well characterized. Importantly, higher concentrations of organic pollutants on ingested MP may be less bioavailable to aquatic organisms than the same chemicals present in dissolved form in the surrounding water. In the current study, the sorption kinetics of two model polycyclic aromatic hydrocarbons (PAHs; fluoranthene and phenanthrene) to MP particles in natural seawater at 10 and 20 °C were studied and the bioavailability of MP-sorbed PAHs to marine copepods investigated. Polyethylene (PE) and polystyrene (PS) microbeads with mean diameters ranging from 10-200 µm were used to identify the role of MP polymer type and size on sorption mechanisms. Additionally, temperature dependence of sorption was investigated. Results indicated that adsorption dominated at lower temperatures and for smaller MP (10 µm), while absorption was the prevailing process for larger MP (100 µm). Monolayer sorption dominated at lower PAH concentrations, while multilayer sorption dominated at higher concentrations. PE particles representing ingestible (10 µm) and non-ingestible (100 µm) MP for the marine copepod species Acartia tonsa and Calanus finmarchicus were used to investigate the availability and toxicity of MP-sorbed PAHs. Studies were conducted under co-exposure conditions where the PAHs were also present in the dissolved phase (Cfree), thereby representing more environmentally relevant exposure scenarios. Cfree reduction through MP sorption was reflected in a corresponding reduction of lethality and bioaccumulation, with no difference observed between ingestible and non-ingestible MP. This indicates that only free dissolved PAHs are significantly bioavailable to copepods under co-exposure conditions with MP-sorbed PAHs. | publishedVersion

The current air pollution by SO₂ due to anthropogenic pressure in Poland was assessed based on sulfur concentrations in pine needles (Pinus sylvestris L.). On 308 monitoring sample plots located in pine stands distributed across Poland, measurements were conducted in mineral soil layers (0–10 cm, 10–40 cm, 40–100 cm) and in the soil organic layer (+5–0 cm). Samples of Scots pine foliage (current-year needles) were then collected, and the sulfur concentration in these needles was determined. Based on these data, a map of the spatial variability of sulfur concentrations in pine needles was drawn. The mean sulfur concentration in the pine needles was 854.8 mg kg⁻¹ in dry mass. Higher SO₂ emissions were noted in regions influenced by industry, such as the Upper Silesia and regions under strong urban pressure. Sulfur concentrations in Scots pine needles were related to the stands' degrees of defoliation. A comparison of the current sulfur concentrations in pine needles from biomonitoring in 2015–2016 with those from previous biomonitoring (in 1983–1985, by Dmuchowski and Bytnerowicz (1995) showed that air quality has improved and SO₂ emissions have decreased.

The current air pollution by SO2due to anthropogenic pressure in Poland was assessed based on sulfurconcentrations in pine needles (Pinus sylvestrisL.). On 308 monitoring sample plots located in pine standsdistributed across Poland, measurements were conducted in mineral soil layers (0e10 cm, 10e40 cm, 40e100 cm) and in the soil organic layer (þ5e0 cm). Samples of Scots pine foliage (current-year needles)were then collected, and the sulfur concentration in these needles was determined. Based on these data,a map of the spatial variability of sulfur concentrations in pine needles was drawn. The mean sulfurconcentration in the pine needles was 854.8 mg kg�1in dry mass. Higher SO2emissions were noted inregions influenced by industry, such as the Upper Silesia and regions under strong urban pressure. Sulfurconcentrations in Scots pine needles were related to the stands' degrees of defoliation. A comparison ofthe current sulfur concentrations in pine needles from biomonitoring in 2015e2016 with those fromprevious biomonitoring (in 1983e1985, byDmuchowski and Bytnerowicz (1995)showed that air qualityhas improved and SO2emissions have decreased. | Sulfur dioxide, Bioindication, Defoliation, Air quality | 100 | 1-8 | 113559

Carbapenems are used as last-resort drugs to treat infections caused by multidrug-resistant bacteria. Despite the increasing number of reports of carbapenem-resistant Enterobacteriaceae (CRE), there is still limited information on their distribution or prevalence in the environment. Our aim was to assess the occurrence of CRE in the Lis river (Portugal) and to characterize the genetic platforms linked to carbapenemase genes. We collected six water samples from sites near a wastewater treatment plant (n = 4 samples) and livestock farms (n = 2). Twenty-four CRE were characterized by BOX element-polymerase chain reaction (BOX-PCR), and thirteen representative isolates were analysed by Pulsed-Field Gel Electrophoresis (PFGE) and by sequencing the 16S rRNA gene. Antimicrobial susceptibility testing, PCR screening for carbapenemase-encoding genes, conjugation experiments and plasmid analysis were performed. Four isolates were chosen for whole-genome sequencing. All water samples contained CRE (4.0 CFU/mL on average). Representative isolates were multidrug-resistant (resistant to ciprofloxacin, trimethoprim-sulfamethoxazole and to all β-lactams tested) and were identified as K. pneumoniae, Enterobacter and Citrobacter. Isolates carried plasmids and harboured carbapenemase-encoding genes: blaKPC₋₃ in K. pneumoniae (n = 9), blaNDM₋₁ in Enterobacter (n = 3) and blaGES₋₅ in Citrobacter (n = 1). Conjugation experiments were successful in two Klebsiella isolates. Enterobacter PFGE profiles grouped in one cluster while Klebsiella were divided in three clusters and a singleton. Whole-genome sequencing analysis revealed blaGES₋₅ within a novel class 3 integron (In3-16) located on an IncQ/pQ7-like plasmid in Citrobacter freundii CR16. blaKPC₋₃ was present on IncFIA-FII pBK30683-like plasmids, which were subsequently confirmed in all K. pneumoniae (n = 9). Furthermore, blaKPC₋₃ was part of a genomic island in K. pneumoniae CR12. In E. roggenkampii CR11, blaNDM₋₁ was on an IncA/C₂ plasmid. The carbapenemase-encoding plasmids harboured other resistance determinants and mobile genetic elements. Our results demonstrate that Lis river is contaminated with CRE, highlighting the need for monitoring antibiotic resistance in aquatic environments, especially to last-resort drugs.

Carbapenems are used as last-resort drugs to treat infections caused by multidrug-resistant bacteria. Despite the increasing number of reports of carbapenem-resistant Enterobacteriaceae (CRE), there is still limited information on their distribution or prevalence in the environment. Our aim was to assess the occurrence of CRE in the Lis river (Portugal) and to characterize the genetic platforms linked to carbapenemase genes. We collected six water samples from sites near a wastewater treatment plant (n = 4 samples) and livestock farms (n = 2). Twenty-four CRE were characterized by BOX element-polymerase chain reaction (BOX-PCR), and thirteen representative isolates were analysed by Pulsed-Field Gel Electrophoresis (PFGE) and by sequencing the 16S rRNA gene. Antimicrobial susceptibility testing, PCR screening for carbapenemase-encoding genes, conjugation experiments and plasmid analysis were performed. Four isolates were chosen for whole-genome sequencing. All water samples contained CRE (4.0 CFU/mL on average). Representative isolates were multidrug-resistant (resistant to ciprofloxacin, trimethoprim-sulfamethoxazole and to all β-lactams tested) and were identified as K. pneumoniae, Enterobacter and Citrobacter. Isolates carried plasmids and harboured carbapenemase-encoding genes: blaKPC-3 in K. pneumoniae (n = 9), blaNDM-1 in Enterobacter (n = 3) and blaGES-5 in Citrobacter (n = 1). Conjugation experiments were successful in two Klebsiella isolates. Enterobacter PFGE profiles grouped in one cluster while Klebsiella were divided in three clusters and a singleton. Whole-genome sequencing analysis revealed blaGES-5 within a novel class 3 integron (In3-16) located on an IncQ/pQ7-like plasmid in Citrobacter freundii CR16. blaKPC-3 was present on IncFIA-FII pBK30683-like plasmids, which were subsequently confirmed in all K. pneumoniae (n = 9). Furthermore, blaKPC-3 was part of a genomic island in K. pneumoniae CR12. In E. roggenkampii CR11, blaNDM-1 was on an IncA/C2 plasmid. The carbapenemase-encoding plasmids harboured other resistance determinants and mobile genetic elements. Our results demonstrate that Lis river is contaminated with CRE, highlighting the need for monitoring antibiotic resistance in aquatic environments, especially to last-resort drugs. | published

Australian tropical freshwaters can experience extreme seasonal variability in rainfall and run off, particularly due to pulse events such as storms and cyclones. This study investigated how seasonal variability in dissolved organic matter (DOM) quality impacted the chronic toxicity of copper to a tropical green alga (Chlorella sp.) in the presence of two concentrations of DOM (low: ∼2 mg C/L; high: ∼10 mg C/L) collected from three tropical waters. Copper speciation and lability were explored using diffusive gradients in thin-films (DGT) and modelled maximum dynamic concentrations (cᵈʸⁿₘₐₓ) using data derived from the Windermere Humic Aqueous Model (WHAM VII). Relationships between copper lability and copper toxicity were assessed as potential tools for predicting toxicity. Copper toxicity varied significantly with DOM concentration, source and season. Copper toxicity decreased with increasing concentrations of DOM, with 50% growth inhibition effect concentrations (EC₅₀) increasing from 1.9 μg Cu/L in synthetic test waters with no added DOM (0.34 mg C/L) up to 63 μg Cu/L at DOM concentrations of 9.9 mg C/L. Copper toxicity varied by up to 2-fold between the three DOM sources and EC₅₀ values were generally lower in the presence of wet season DOM compared to dry season DOM. Linear relationships between DGT-labile copper and dissolved copper were significantly different between DOM source, but not concentration or season. Modelled cᵈʸⁿₘₐₓ consistently under-predicted labile copper in high DOM treatments compared to DGT measurements but performed better in low DOM treatments, indicating that this method is DOM-concentration dependent. Neither speciation method was a good surrogate for copper toxicity in the presence of different sources of natural DOM. Our findings show that DOM source and season, not just DOM concentration, affect copper toxicity to freshwater biota. Therefore, DOM quality should be considered as a toxicity-modifying factor for future derivation of bioavailability-based site-specific water quality guideline values.

Australian tropical freshwaters can experience extreme seasonal variability in rainfall and run off, particularly due to pulse events such as storms and cyclones. This study investigated how seasonal variability in dissolved organic matter (DOM) quality impacted the chronic toxicity of copper to a tropical green alga (Chlorella sp.) in the presence of two concentrations of DOM (low: ∼2 mg C/L; high: ∼10 mg C/L) collected from three tropical waters. Copper speciation and lability were explored using diffusive gradients in thin-films (DGT) and modelled maximum dynamic concentrations (cdynmax) using data derived from the Windermere Humic Aqueous Model (WHAM VII). Relationships between copper lability and copper toxicity were assessed as potential tools for predicting toxicity. Copper toxicity varied significantly with DOM concentration, source and season. Copper toxicity decreased with increasing concentrations of DOM, with 50% growth inhibition effect concentrations (EC50) increasing from 1.9 μg Cu/L in synthetic test waters with no added DOM (0.34 mg C/L) up to 63 μg Cu/L at DOM concentrations of 9.9 mg C/L. Copper toxicity varied by up to 2-fold between the three DOM sources and EC50 values were generally lower in the presence of wet season DOM compared to dry season DOM. Linear relationships between DGT-labile copper and dissolved copper were significantly different between DOM source, but not concentration or season. Modelled cdynmax consistently under-predicted labile copper in high DOM treatments compared to DGT measurements but performed better in low DOM treatments, indicating that this method is DOM-concentration dependent. Neither speciation method was a good surrogate for copper toxicity in the presence of different sources of natural DOM. Our findings show that DOM source and season, not just DOM concentration, affect copper toxicity to freshwater biota. Therefore, DOM quality should be considered as a toxicity-modifying factor for future derivation of bioavailability-based site-specific water quality guideline values.