Complex and organic-rich solid substrates such as sludge and soil have been shown to be contaminated by microplastics; however, methods for extracting plastic particles have not yet been systemically tested or standardized. This study investigated four main protocols for the removal of organic material during analysis of microplastics from complex solid matrices: oxidation using HO, Fenton's reagent, and alkaline digestion with NaOH and KOH. Eight common polymer types were used to assess the influence of reagent exposure on particle integrity. Organic matter removal efficiencies were established for test sludge and soil samples. Fenton's reagent was identified as the optimum protocol. All other methods showed signs of particle degradation or resulted in an insufficient reduction in organic matter content. A further validation procedure revealed high microplastic extraction efficiencies for particles with different morphologies. This confirmed the suitability of Fenton's reagent for use in conjunction with density separation for extracting microplastics. This approach affords greater comparability with existing studies that utilize a density-based technique. Recommendations for further method optimization were also identified to improve the recovery of microplastic from complex, organic-rich environmental samples.
The presence of microplastics (MPs) in the environment is a problem of growing concern. While research has focused on MP occurrence and impacts in the marine environment, very little is known about their release on land, storage in soils and sediments and transport by run-off and rivers. This study describes a first theoretical assessment of these processes. A mathematical model of catchment hydrology, soil erosion and sediment budgets was upgraded to enable description of MP fate. The Thames River in the UK was used as a case study. A general lack of data on MP emissions to soils and rivers and the mass of MPs in agricultural soils, limits the present work to serve as a purely theoretical, nevertheless rigorous, assessment that can be used to guide future monitoring and impact evaluations. The fundamental assumption on which modelling is based is that the same physical controls on soil erosion and natural sediment transport (for which model calibration and validation are possible), also control MP transport and storage. Depending on sub-catchment soil characteristics and precipitation patterns, approximately 16-38% of the heavier-than-water MPs hypothetically added to soils (e.g. through routine applications of sewage sludge) are predicted to be stored locally. In the stream, MPs < 0.2 mm are generally not retained, regardless of their density. Larger MPs with densities marginally higher than water can instead be retained in the sediment. It is, however, anticipated that high flow periods can remobilize this pool. Sediments of river sections experiencing low stream power are likely hotspots for deposition of MPs. Exposure and impact assessments should prioritize these environments.
Surface seawater and boundary layer atmospheric samples were collected on the FS Polarstern during cruise ARKXX in the North Atlantic and Arctic Ocean in 2004. Samples were analyzed for persistent organic pollutants (POPs), with a focus on organochlorine pesticides, including hexachlorocyclohexanes (HCHs), chlordanes, DDTs, hexachlorobenzene (HCB), and polycyclic aromatic hydrocarbons. In addition, the enantiomer fractions (EFs) of pesticides, notably alpha-HCH and cis-chlordane (CC), were determined. Concentrations of dissolved HCB increased from near Europe (approximately 1-2 pg/L) toward the high Arctic (4-10 pg/L). For dissolved HCB, strongest correlations were obtained with the average air or water temperature during sampling, not latitude. In the western Arctic Ocean, surface waters with elevated concentrations of HCB (5-10 pg/ L) were flowing out of the Arctic Ocean as part of the East Greenland current In contrast to dissolved compounds, atmospheric POPs did not display trends with temperature. Air-water exchange gradients suggested net deposition for all compounds, though HCB was closest to air-water equilibrium. EFs for alpha-HCH in seawater ranged from 0.43 to 0.50, except for two samples from 75 degrees N in the East Greenland Sea, with EFs of 0.31 and 0.37. Lowest EF (0.47) for CC were also at 75 degrees N, other samples had EFs from 0.49 to 0.52. It is suggested that samples from around 75 degrees N in the Greenland Gyre represented a combination of surface and older/deeper Arctic water.
Air and seawater samples were collected on board the RV Polarstern during a cruise from Bremerhaven, Germany to Cape Town, South Africa from October-November 2005. Broad latitudinal trends were observed with the lowest sigma27PCB air concentration (approximately 10 pg m(-3)) in the South Atlantic and the highest (approximately 1000 pg m(-3)) off the west coast of Africa. Sigma(ICES)PCBs ranged from 3.7 to 220 pg m(-3) in air samples and from 0.071 to 1.7 pg L(-1) in the dissolved phase seawater samples. Comparison with other data from cruises in the Atlantic Ocean since 1990 indicate little change in air concentrations over the remote open ocean. The relationship of gas-phase partial pressure with temperature was examined using the Clausius-Clapeyron equation; significant temperature dependencies were found for all PCBs over the South Atlantic, indicative of close air-water coupling. There was no temperature dependence for atmospheric PCBs overthe North Atlantic, where concentrations were controlled by advection of contaminated air masses. Due to large uncertainties in the Henry's Law Constant (HLC), fugacity fractions and air-water exchange fluxes were estimated using different HLCs reported in the literature. These suggest that conditions are close to air-water equilibrium for most of the ocean, but net deposition is dominating over volatilization in parts of the transect. Generally, the tri- and tetrachlorinated homologues dominated the total flux (> 70%). Total PCB fluxes (28, 52, 118, 138, and 153) ranged from -7 to 0.02 ng m(-2) day(-1).
Polycyclic aromatic hydrocarbons (PAHs) were simultaneously measured in air and surface seawater between 49 degrees N and 25 degrees S in the open Atlantic Ocean. Elevated concentrations of PAHs (sigma10 PAHs approximately 1.4-2.5 ng m(-3) air, and 0.7-1 ng L(-1) seawater) occurred in the Biscay Bay and off the northwest coast of Africa. The unexpectedly high concentrations off NW Africa were discussed assessing the possible contribution of the emerging oil industry along the African shore, the role of biomass burning and natural sources of PAHs. In the southern Atlantic, concentrations of PAHs were close to detection limits (sigma10 PAHs approximately 0.02-0.5 ng m(-3) air, and 0.06-0.5 ng L(-1) seawater) and showed decreasing trends with increasing latitudes. Correlations of PAHs' partial pressures versus inverse temperature were not significant in contrast to results for polychlorinated biphenyls from the same transect. This could have been due to the importance of ongoing primary sources and the shorter atmospheric life-times of PAHs. Air-water fugacity ratios (fa/fw) were calculated for selected compounds. They were close to 1 for fluoranthene and pyrene in remote open ocean areas suggesting air-water partitioning near equilibrium. Ratios for anthracene and phenanthrene were < 0.3 in the remote tropical Atlantic, suggesting net volatilization.
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