Phytoplankton may serve as a key entry for methylmercury (MeHg) into aquatic food webs however very few studies have quantified the bioconcentration of MeHg in marine phytoplankton from seawater, particularly for non‐diatoms. Experiments using 203Hg to measure MeHg uptake rates and concentration factors in six marine phytoplankton species belonging to different algal classes were conducted and the influence of light, temperature, and nutrient conditions on MeHg bioaccumulation were determined. All algal species greatly concentrated MeHg out of seawater, with volume concentration factors (VCFs) ranging from 0.2 × 105 to 6.4 × 106. VCFs were directly related to cellular surface area‐to‐volume ratios. Most of the cellular MeHg was found in the cytoplasm. Temperature, light, and nutrient additions did not directly affect MeHg uptake in most species, with the exception that the dinoflagellate Prorocentrum minimum displayed significantly greater uptake per cell at 18°C than at 4°C, suggesting an active uptake for this species. Passive transport seemed to be the major pathway for most phytoplankton to acquire MeHg and was related to the surface area‐to‐volume ratio of algal cells. Environmental conditions that promoted cell growth resulted in more total MeHg associated with cells, but with lower concentrations per unit biomass due to biodilution. The very high bioconcentration of MeHg in marine phytoplankton is by far the largest bioconcentration step in marine food chains and variations in algal uptake may account for differences in the amount of MeHg that ultimately builds up in different marine ecosystems.
Although most manufacturers stopped using long-chain per- and polyfluoroalkyl substances (PFASs), including perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), short-chain PFASs are still widely employed. Short-chain PFASs are less known in terms of toxicity and have different adsorption behavior from long-chain PFASs. Previous studies have shown electrostatic interaction with the adsorbent to be the dominant mechanism for the removal of short-chain PFASs. In this study, we designed a high charge density cationic quaternized nanocellulose (QNC) to enhance the removal of both short- and long-chain PFASs from contaminated water. Systematic batch adsorption tests were conducted using the QNC adsorbent to compare its efficiency against PFASs with varying chain lengths and functional groups. From the kinetic study, PFBA (perfluorobutanoic acid), PFBS (perfluorobutanesulfonic acid) and PFOS showed rapid adsorption rates, which reached near equilibrium values (>95% of removal) between 1 min to 15 min, while PFOA required a relatively longer equilibration time of 2 h (it obtained 90% of removal within 15 min). According to the isotherm results, the maximum adsorption capacity (Qm) of the QNC adsorbent exhibited the following trend: PFOS (Qm = 559 mg g−1 or 1.12 mmol g−1) > PFOA (Qm = 405 mg g−1 or 0.98 mmol g−1) > PFBS (Qm = 319 mg g−1 or 1.06 mmol g−1) > PFBA (Qm = 121 mg g−1 or 0.57 mmol g−1). This adsorption order generally matches the hydrophobicity trend among four PFASs associated with both PFAS chain length and functional group. In competitive studies, pre-adsorbed short-chain PFASs were quickly desorbed by long-chain PFASs, suggesting that the hydrophobicity of the molecule played an important role in the adsorption process on to QNC. Finally, the developed QNC adsorbent was tested to treat PFAS-contaminated groundwater, which showed excellent removal efficiency (>95%) for long-chain PFASs (C7–C9) even at a low adsorbent dose of 32 mg L−1. However, short-chain PFASs (i.e., PFBA and perfluoropentanoic acid (PFPeA)) were poorly removed by the QNC adsorbent (0% and 10% removal, respectively) due to competing constituents in the groundwater matrix. This was further confirmed by controlled experiments that revealed a drop in the performance of QNC to remove short-chain PFASs at elevated ionic strength (NaCl), but not for long-chain PFASs, likely due to charge neutralization of the anionic functional group of PFASs by inorganic cations. Overall, the QNC adsorbent featured improved PFAS adsorption capacity at almost two-fold of PFAS removal by granular activated carbons, especially for short-chain PFASs. We believe, QNC can complement the use of common treatment methods such as activated carbon or ionic exchange resin to remove a wide range of PFAS pollutants, heading towards the complete remediation of PFAS contamination.
Many environmentally relevant poly-/perfluoroalkyl substances (PFASs) including perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) exist in different isomeric (branched and linear) forms in the natural environment. The isomeric distribution of PFASs in the environment and source waters is largely controlled by the source of contamination and varying physicochemical properties imparted by their structural differences. For example, branched isomers of PFOS are relatively more reactive and less sorptive compared to the linear analogue. As a result, the removal of branched and linear PFASs during water treatment can vary, and thus the isomeric distribution in source waters can influence the overall efficiency of the treatment process. In this paper, we highlight the need to consider the isomeric distribution of PFASs in contaminated matrices while designing appropriate remediation strategies. We additionally summarize the known occurrence and variation in the physicochemical properties of PFAS isomers influencing their detection, fate, toxicokinetics, and treatment efficiency.
10 November 2016 in Environmental Science & Technology