Humic acid (HA) coated Fe 3 O 4 nanoparticles (Fe 3 O 4 /HA) were developed for the removal of toxic Hg(II), Pb(II), Cd(II), and Cu(II) from water. Fe 3 O 4 /HA were prepared by a coprecipitation procedure with cheap and environmentally friendly iron salts and HA. TOC and XPS analysis showed the as-prepared Fe 3 O 4 / HA contains ∼11% (w/w) of HA which are fractions abundant in O and N-based functional groups. TEM images and laser particle size analysis revealed the Fe 3 O 4 /HA (with ∼10 nm Fe 3 O 4 cores) aggregated in aqueous suspensions to form aggregates with an average hydrodynamic size of ∼140 nm. With a saturation magnetization of 79.6 emu/g, the Fe 3 O 4 /HA can be simply recovered from water with magnetic separations at low magnetic field gradients within a few minutes. Sorption of the heavy metals to Fe 3 O 4 /HA reached equilibrium in less than 15 min, and agreed well to the Langmuir adsorption model with maximum adsorption capacities from 46.3 to 97.7 mg/g. The Fe 3 O 4 /HA was stable in tap water, natural waters, and acidic/ basic solutions ranging from 0.1 M HCl to 2 M NaOH with low leaching of Fe (e3.7%) and HA (e5.3%). The Fe 3 O 4 /HA was able to remove over 99% of Hg(II) and Pb(II) and over 95% of Cu(II) and Cd(II) in natural and tap water at optimized pH. Leaching back of the Fe 3 O 4 /HA sorbed heavy metals in water was found to be negligible.
As the most complex halogenated contaminants, short chain chlorinated paraffins (SCCPs) are scarcely reported in marine environments. In this work, a total of 117 surficial sediment (0-3 cm) samples and two sediment cores were collected from the Chinese Bohai and Yellow Seas to systematically study the spatial and temporal trends of SCCPs at a large scale in the Chinese marine environment. Total SCCP concentrations in the surficial sediments were in the range of 14.5-85.2 ng g(-1) (dry weight, d.w.) with an average level of 38.4 ng g(-1) d.w. Spatial distribution showed a decreasing trend with the distance from the coast to the open waters. Compositional pattern analysis suggested that C10 was the most predominant homologue group, followed by C11, C12, and C13 homologue groups. The concentrations of total SCCPs in sediment cores ranged from 11.6 to 94.7 ng g(-1) d.w. for YS1 and from 14.7 to 195.6 ng g(-1) d.w. for YS2, with sharp rise from the early 1950s to present based on (210)Pb dating technique. The historical records in cores correspond well to the production and usage changes of CPs in China. Multivariate regression statistics indicate TOC, latitude and longitude are the major factors influencing surficial SCCP levels in the Chinese East Seas by combining analysis with the data from the East China Sea (R(2) = 0.332, p < 0.01). These findings indicated that the sources of SCCPs were mainly from river outflows via ocean current and partly from atmospheric depositions by East Asian monsoon in the sampling areas.
Short chain chlorinated paraffins (SCCPs) are high production volume chemicals in China and found to be widely present in the environment. In this study, fifty-one surface sediments and two sediment cores were collected from the East China Sea to study their occurrence, distribution patterns and potential transport in the marginal sea. SCCPs were found in all surface sediments and ranged from 5.8 to 64.8 ng/g (dry weight, d.w.) with an average value of 25.9 ng/g d.w. A general decreasing trend with distance from the coast was observed, but the highest value was found in a distal mud area far away from the land. The C10 homologue was the most predominant carbon chain group, followed by C11, C12, and C13 homologue groups. Significant linear relationship was found between total organic carbon (TOC) and total SCCP concentrations (R(2) = 0.51, p < 0.05). Spatial distributions and correlation analysis indicated that TOC, riverine input, ocean current, and atmospheric deposition played an important role in controlling SCCP accumulation in marine sediments. Vertical profiles of sediment cores showed that SCCP concentrations decreased from surface to the depth of 36 cm, and then slightly increased again with depth, which showed a significant positive correlation with TOC and chlorine contents (Cl%). The results suggest that SCCPs are being regionally or globally distributed by long-range atmospheric or ocean current transport.
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