Interlaboratory Comparison of Extractable Organofluorine Measurements in Groundwater and Eel (Anguilla rostrata): Recommendations for Methods Standardization.

Research on per- and polyfluoroalkyl substances (PFAS) frequently incorporates organofluorine measurements, particularly because they could support a class-based approach to regulation. However, standardized methods for organofluorine analysis in a broad suite of matrices are currently unavailable, including a method for extractable organofluorine (EOF) measured using combustion ion chromatography (CIC). Here, we report the results of an international interlaboratory comparison. Seven laboratories representing academia, government, and the private sector measured paired EOF and PFAS concentrations in groundwater and eel (Anguilla rostrata) from a site contaminated by aqueous film-forming foam. Among all laboratories, targeted PFAS could not explain all EOF in groundwater but accounted for most EOF in eel. EOF results from all laboratories for at least one replicate extract fell within one standard deviation of the interlaboratory mean for groundwater and five out of seven laboratories for eel. PFAS spike mixture recoveries for EOF measurements in groundwater and eel were close to the criterion (±30%) for standardized targeted PFAS methods. Instrumental operation of the CIC such as replicate sample injections was a major source of measurement uncertainty. Blank contamination and incomplete inorganic fluorine removal may introduce additional uncertainties. To elucidate the presence of unknown organofluorine using paired EOF and PFAS measurements, we recommend that analysts carefully consider confounding methodological uncertainties such as differences in precision between measurements, data processing steps such as blank subtraction and replicate analyses, and the relative recoveries of PFAS and other fluorine compounds.

Wastewater-Aged Silver Nanoparticles in Single and Combined Exposures with Titanium Dioxide Affect the Early Development of the Marine Copepod Tisbe battagliai.

In this study, the effects of aged Ag and TiO2 nanoparticles (NPs), individually and as a mixture, in wastewater relative to their pristine counterparts on the development of the copepod nauplii (Tisbe battagliai) were investigated. NP behavior in synthetic wastewater and seawater was characterized during aging and exposure. A delayed development and subsequent mortality were observed after 6 days of exposure to aged Ag NPs, with a twofold decrease in EC50 (316 µg/L) compared to pristine NPs (EC50 640 µg/L) despite the similar dissolved Ag concentrations measured for aged and pristine Ag NPs (441 and 378 µg/L, respectively). In coexposures with TiO2 NPs, higher dissolved Ag levels were measured for aged NPs (238.3 µg/L) relative to pristine NPs (98.57 µg/L). Coexposure resulted in a slight decrease (15%) in the Ag NP EC50 (270 µg/L) with a 1.9-fold increase in the Ag NP retained within the organisms after depuration (2.82% retention) compared to Ag NP single exposures as measured with sp-ICP-MS, suggesting that the particles are still bioavailable despite the heteroaggregation observed between Ag, Ti NPs, and wastewater components. This study shows that the presence of TiO2 NPs can affect the stability and toxicity of Ag NPs in complex media that cannot be predicted solely based on ionic, total, or nanoparticulate concentrations, and the need for studying NP interactions in more complex matrices is highlighted.

Ecotoxicological Effects of Transformed Silver and Titanium Dioxide Nanoparticles in the Effluent from a Lab-Scale Wastewater Treatment System.

In this study, a lab-scale wastewater treatment plant (WWTP), simulating biological treatment, received 10 µg/L Ag and 100 µg/L TiO2 nanoparticles (NPs) for 5 weeks. NP partitioning was evaluated by size fractionation (>0.7 µm, 0.1-0.7 µm, 3 kDa-0.1 µm, < 3 kDa) using inductively coupled plasma mass spectrometry (ICP-MS), single particle ICP-MS and transmission electron microscopy. The ecotoxicological effects of the transformed NPs in the effluent were assessed using a battery of marine and freshwater bioassays (algae and crustaceans) and an in vitro gill cell line model (RTgill-W1). TiO2 aggregates were detected in the effluent, whereas Ag NPs (0.1-0.22 µg/L) were associated with S, Cu, Zn. Fractionation showed that >80% of Ag and Ti were associated with the effluent solids. Increased toxicity was observed during weeks 2-3 and the effects were species-dependent; with marine epibenthic copepods and algae being the most sensitive. Increased reactive oxygen species formation was observed in vitro followed by an increase in epithelial permeability. The effluent affected the gill epithelium integrity in vitro and impacted defense pathways (upregulation of multixenobiotic resistance genes). To our knowledge, this is the first study to combine a lab-scale activated sludge WWTP with extensive characterization techniques and ecotoxicological assays to study the effects of transformed NPs in the effluent.

Lead Sources to the Amundsen Sea, West Antarctica.

The global prevalence of industrial lead (Pb) contamination was exemplified decades ago by the predominance of anthropogenic Pb in samples of Antarctic surface ice and in Southern Ocean surface waters. Decreases in environmental Pb contamination corresponding with the near-global phase-out of leaded automobile gasoline beginning in the 1970s have since been observed. Measurements of Pb concentration in snow and ice core samples from Antarctica show that recent fluxes of industrial Pb to Antarctica have similarly declined. Here, we present measurements of Pb concentrations and isotopic compositions in seawater and surface sediments from the Amundsen Sea continental shelf including the Amundsen Sea Polynya. Both sets of measurements show that most (∼60-95%) of the Pb at our sites, at the time of sampling, is natural in source: that is, derived from the weathering of Antarctic continental rocks. These fluxes of natural Pb then become entrained into polynya waters either from sediment resuspension or from the transport of sediment-laden glacial melt waters to the polynya.

Nano zerovalent Fe did not reduce metal(loid) leaching and ecotoxicity further than conventional Fe grit in contrasting smelter impacted soils: A 1-year field study.

The majority of the studies on nanoscale zero-valent iron (nZVI) are conducted at a laboratory-scale, while field-scale evidence is scarce. The objective of this study was to compare the metal(loid) immobilization efficiency of selected Fe-based materials under field conditions for a period of one year. Two contrasting metal(loid) (As, Cd, Pb, Zn) enriched soils from a smelter-contaminated area were amended with sulfidized nZVI (S-nZVI) solely or combined with thermally stabilized sewage sludge and compared to amendment with microscale iron grit. In the soil with higher pH (7.5) and organic matter content (TOC = 12.7 %), the application of amendments resulted in a moderate increase in pH and reduced As, Cd, Pb, and Zn leaching after 1-year, with S-nZVI and sludge combined being the most efficient, followed by iron grit and S-nZVI alone. However, the amendments had adverse impacts on microbial biomass quantity, S-nZVI being the least damaging. In the soil with a lower pH (6.0) and organic matter content (TOC = 2.3 %), the results were mixed; 0.01 M CaCl2 extraction data showed only S-nZVI with sludge as remaining effective in reducing extractable concentrations of metals; on the other hand, Cd and Zn concentrations were increased in the extracted soil pore water solutions, in contrast to the two conventional amendments. Despite that, S-nZVI with sludge enhanced the quantity of microbial biomass in this soil. Additional earthworm avoidance data indicated that they generally avoided soil treated with all Fe-based materials, but the presence of sludge impacted their preferences somewhat. In summary, no significant differences between S-nZVI and iron grit were observed for metal(loid) immobilization, though sludge significantly improved the performance of S-nZVI in terms of soil health indicators. Therefore, this study indicates that S-nZVI amendment of soils alone should be avoided, though further field evidence from a broader range of soils is now required.

Model predictions of copper speciation in coastal water compared to measurements by analytical voltammetry.

Trace metal toxicity to aquatic biota is highly dependent on the metals chemical speciation. Accordingly, metal speciation is being incorporated in to water quality criteria and toxicity regulations using the Biotic Ligand Model (BLM) but there are currently no BLM for biota in marine and estuarine waters. In this study, I compare copper speciation measurements in a typical coastal water made using Competitive ligand exchange-adsorptive cathodic stripping voltammetry (CLE-ACSV) to model calculations using Visual MINTEQ. Both Visual MINTEQ and BLM use similar programs to model copper interactions with dissolved organic matter-DOM (i.e., the Stockholm Humic Model and WHAM-Windermere Humic Aqueous Model, respectively). The total dissolved (<0.4 µm filter) copper concentration, [CuT] in the study sites ranged from <10 nM close to the open Baltic Sea to ca. 50 nM in the vicinity of a marina in the Stockholm Archipelago. The corresponding free copper concentration [Cu2+], measured by CLE-ACSV ranged from 10­13.2 M to 10­12.0 M for the reference and marina sites, respectively, whereas the corresponding [Cu2+] modeled calculations ranged from 10­12.5 M to 10­11.6 M. The low copper to DOM ratios (similar to 0.0004 mg Cu per mg DOC) in these coastal waters ensured that ambient dissolved copper was overwhelmingly chelated to strong Cu­binding ligands (12 < log KCuL1,Cu2+Cond >14). The modeled [Cu2+] could be fitted to the experimental values better after the conditional stability constant for copper binding to fulvic acid (FA) complexes in DOM in the SHM was adjusted to account for higher concentration of strong Cu-binding sites in FA.

Multivariate optimization of a two-way technique for extraction of pharmaceuticals in surface water using a combination of membrane assisted solvent extraction and a molecularly imprinted polymer.

This work demonstrates development and evaluation of a two-way technique based on the combination of membrane assisted solvent extraction and a molecularly imprinted polymer (MASE-MIP) for selective and efficient extraction of five selected pharmaceuticals belonging to five different therapeutic classes. The pharmaceuticals were extracted from surface water samples followed by liquid chromatography-quadrupole time-of-flight mass spectrometry (LC-qTOF/MS) determination. A central composite design was applied to optimize the influence of the sample salt content, the stirring rate, the stirring time and the amount of MIP on the extraction of an anticonvulsant (carbamazepine), a cardiac stimulant (etilefrine), a muscle relaxant (methocarbamol), an antiretroviral (nevirapine) and an antidepressant (venlafaxine) from surface water. Optimization of the analytical method was performed by spiking water with a mixture of all five pharmaceuticals at 500 ng mL-1. Optimum extraction conditions for a sample volume of 18 mL were found to be 5 g of salt content, a stirring rate of 400 rpm, an extraction time of 60 min and 50 mg of MIP. The MASE-MIP-LC-qTOF/MS method gave detection and quantification limits ranging from 0.09 to 0.20 ng mL-1 and 0.31-0.69 ng mL-1, respectively. The spiked river water samples yielded recoveries ranging from 38 to 91% for the selected model compounds belonging to the five classes of pharmaceuticals. Upon the application of the developed analytical method in water analysis, all selected pharmaceuticals were detected in South African river water with nevirapine and venlafaxine being more prominent attaining the maximum concentrations of 1.64 and 2.48 ng mL-1, respectively.

Distribution pattern of mercury in northern Barents Sea and Eurasian Basin surface sediment.

Marine sediment is a significant sink for the global pollutant mercury. In a rapidly changing Arctic region, mercury (Hg) bioaccumulation in the marine ecosystem remains a prominent environmental issue. Here, we report surface sediment (0-2 cm) concentrations of Hg and other toxic elements of interest (Cr, Ni, Zn, Cu, As, Cd, Pb) in the northern Barents Sea and Eurasian Basin. We observed average Hg concentrations of 65 ± 23 ng/g with the highest concentration of 116 ng/g in the Eurasian Basin. Our calculated enrichment factors suggest low anthropogenic enrichment for mercury, chromium, nickel, and copper. Mercury and trace element geographic patterns are best explained by the origin and transportation of fine grain sediment towards the Eurasian Basin, with scavenging by both particulate organic carbon and metal oxides as significant delivery mechanisms.

Effect of organic complexation on copper accumulation and toxicity to the estuarine red macroalga Ceramium tenuicorne: a test of the free ion activity model.

Current water quality criteria (WQC) regulations on copper toxicity to biota are still based on total dissolved (<0.4 µm membrane filter) copper concentrations with a hardness modification for freshwaters. There are however ongoing efforts to incorporate metal speciation in WQC and toxicity regulations (such as the biotic ligand model-BLM) for copper and other metals. Here, we show that copper accumulation and growth inhibition of the Baltic macroalga Ceramium tenuicorne exposed to copper in artificial seawater at typical coastal and estuarine DOC concentrations (similar to 2-4 mg/L-C as fulvic acid) are better correlated to weakly complexed and total dissolved copper concentrations rather than the free copper concentration [Cu2+]. Our results using a combination of competitive ligand exchange-adsorptive cathodic stripping voltammetry (CLE-ACSV) measurements and model calculations (using visual MINTEQ incorporating the Stockholm Humic Model) show that copper accumulation in C. tenuicorne only correlates linearly well to [Cu2+] at relatively high [Cu2+] and in the absence of fulvic acid. Thus the FIAM fails to describe copper accumulation in C. tenuicorne at copper and DOC concentrations typical of most marine waters. These results seem to indicate that at ambient total dissolved copper concentration in coastal and estuarine waters, C. tenuicorne might be able to access a sizable fraction of organically complexed copper when free copper concentration to the cell membrane is diffusion limited.

Dissolved silver in the Baltic Sea.

The increased use of silver as a biocide in nanoparticle formulations has heightened concern on possible environmental implications owing to its toxicity. There is however very little data on the concentration levels of silver in marine and freshwaters. Here, I report data on dissolved (<0.4 µm filter) silver concentration in the surface waters of the Baltic Sea, the first such data reported for a European coastal water body. Levels of dissolved silver in the Baltic are comparable to those reported for other American estuarine waters and range from non-detectable in the open Baltic Sea Proper (<1 pM) to 9.4 pM (1 ng/L) in the Stockholm Archipelago, with a mean of 2.8 pM (0.2 ng/L). Inputs from wastewater treatment are clearly discernable and might constitute the main source of silver to the Stockholm Archipelago and possibly the Baltic Sea Proper.

Influence of salinity and organic matter on the toxicity of Cu to a brackish water and marine clone of the red macroalga Ceramium tenuicorne.

Cu is a major active component in anti-fouling paints, which may reach toxic levels in areas with intense boat traffic and therefore is a metal of environmental concern. The bioavailability of metals is influenced by factors such as salinity and organic matter measured as total organic carbon (TOC). The influence of these two factors was studied, with a focus on brackish water conditions, by exposing a marine and a brackish water clone of the red macroalga Ceramium tenuicorne to Cu in different combinations of artificial seawater (salinity 5-15‰) and TOC (0-4 mg/L) in the form of fulvic acid (FA). In addition, the toxicity of Cu to both clones was compared in salinity 10‰ and 15‰. The results show that by increasing TOC from 0 to 2 and 4 mg/L, Cu was in general less toxic to both algal clones at all salinities tested (p<0.05). The effect of salinity on Cu toxicity was not as apparent, both a positive and negative effect was observed. The brackish water clone showed generally to be more sensitive to Cu in salinity 10‰ and 15‰ than the marine counterpart. In conclusion, FA reduced the Cu toxicity overall. The Cu tolerance of both strains at different salinities may reflect their origin and their adaptations to marine and brackish water.

Benthic community status and mobilization of Ni, Cu and Co at abandoned sea deposits for mine tailings in SW Norway.

During 1960-94 tailings from an ilmenite mine in southwest Norway were placed in sea deposits in a sheltered fjord and a more exposed coastal basin. In 2015 both deposit sites were sampled to assess the state of metal contamination and macrobenthic communities 20-30 years after deposition was ended. The results showed that nickel and copper still exceeded environmental quality standards in sediment and pore water from the 0-1 cm layer, and fluxes of nickel, copper and cobalt to the overlying water was high compared to adjacent reference stations. Fauna communities were classified as good, but moderate disturbance was recorded along an environmental gradient defined by depth and tailings-induced parameters such as particle size and copper. The results were interpreted in terms of current discharges, biological sediment reworking and near-surface leaching of metal sulphides. No evidence was found for recycling of metals from tailings buried below the bioturbated surface layer.

Petroleum oil and mercury pollution from shipwrecks in Norwegian coastal waters.

Worldwide there are tens of thousands of sunken shipwrecks lying on the coastal seabed. These potentially polluting wrecks (PPW) are estimated to hold 3-25milliont of oil. Other hazardous cargo in PPW includes ordnance, chemicals and radioactive waste. Here, we present and discuss studies on mercury (Hg) and oil pollution in coastal marine sediment caused by two of the >2100 documented PPW in Norwegian marine waters. The German World War II (WWII) submarine (U-864) lies at about 150m below the sea surface, near the Norwegian North Sea island of Fedje. The submarine is estimated to have been carrying 67t of elemental Hg, some of which has leaked on to surrounding sediment. The total Hg concentration in bottom surface sediment within a 200m radius of the wreckage decreases from 100g/kgd.w. at the wreckage hotspot to about 1mg/kgd.w. at 100m from the hotspot. The second wreck is a German WWII cargo ship (Nordvard), that lies at a depth of ca. 30m near the Norwegian harbor of Moss. Oil leakage from Nordvard has contaminated the bottom coastal sediment with polycyclic aromatic hydrocarbons (PAH). The findings from this study provide useful insight to coastal administration authorities involved in assessing and remediating wreck-borne pollution from any of the tens of thousands of sunken shipwrecks.

Effects of organic matter addition on methylmercury formation in capped and uncapped marine sediments.

In situ subaqueous capping (ISC) of contaminated marine sediments is frequently proposed as a feasible and effective mitigation option. However, though effective in isolating mercury species migration into overlying water, capping can also alter the location and extent of biogeochemical zones and potentially enhance methylmercury (MeHg) formation in Hg-contaminated marine sediments. We carried out a boxcosm study to investigate whether the addition of organic carbon (OC) to Hg-contaminated marine sediments beneath an in situ cap would initiate and/or enhance MeHg formation of the inorganic Hg present. The study was motivated by ongoing efforts to remediate ca. 30,000 m(2) of Hg-contaminated seabed sediments from a Hg spill from the U864 WWII submarine wreck. By the time of sinking, the submarine is assumed to have been holding a cargo of ca. 65 tons of liquid Hg. Natural organic matter and petroleum hydrocarbons from fuels and lubricants in the wreck are potential sources of organic carbon that could potentially fuel MeHg formation beneath a future cap. The results of our study clearly demonstrated that introduction of algae OC to Hg-contaminated sediments, triggered high rates of MeHg production as long a there was sufficient OC. Thus, MeHg production was limited by the amount of organic carbon available. The study results also confirmed that, within the six-month duration of the study and in the absence of bioturbating fauna, a 3-cm sediment clay cap could effectively reduce fluxes of Hg species to the overlying water and isolate the Hg-contaminated sediments from direct surficial deposition of organic matter that could potentially fuel methylation.

Comparison of copper speciation in estuarine water measured using analytical voltammetry and supported liquid membrane techniques.

The supported liquid membrane (SLM) is a promising separation and preconcentration technique that is well-suited for trace metal speciation in natural waters. The technique is based on the selective complexation of metal ions by a hydrophobic ligand (carrier) dissolved in a water-immiscible organic solvent immobilized in a porous, inert membrane. This membrane separates two aqueous solutions: the test (or donor) solution and the strip (or acceptor) solution. The metal carrier complex is transported by diffusion across the membrane from the source to the strip solution where metal ions are back-extracted. The technique offers great potential to tune the selectivity by incorporating different complexing ligands in the membrane. A SLM was used to analyze the dissolved (<0.45 microm) copper speciation from two sites in the San Francisco Bay estuary; Dumbarton Bridge, [Cu]total approximately 27 nM, and San Bruno Shoals, [Cu]total approximately 23 nM. The sites were also characterized independently by differential pulse anodic stripping voltammetry (DPASV) using a Nafion-coated thin mercury film electrode (NCTMFE). The SLM employed 10 mM lasalocid, a naturally occurring carboxylic polyether ionophore, in nitrophenyl octyl ether (NPOE) asthe membrane complexing ligand, supported by a microporous, polypropylene, hydrophobic membrane. This is the first study where SLM technique has been compared with an independent speciation technique in marine waters. Results of copper speciation measurements from Dumbarton Bridge, a site in South San Francisco Bay where copper speciation has been well-characterized in previous studies using various voltammetric techniques, indicated that only about 3% (0.9 nM) of the total dissolved copper was SLM labile. The corresponding DPASV labile copper fraction was <0.4% (<0.1 nM) of total dissolved copper. The concentration of total copper binding ligands measured by the membrane technique was 471 nM as compared to 354 nM measured by DPASV, more than 1 order of magnitude higher than the total dissolved copper concentration. The SLM measurements were consistent with earlier copper speciation measurements that were made in South San Francisco Bay using other voltammetric stripping techniques.