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[en] A better understanding of anthropogenic impact can help assess the diffuse trace metal accumulation in the agricultural environment. In this study, both river sediments and background soils were collected from a case study area in Northeast China and analyzed for total concentrations of six trace metals, four major elements and three lead isotopes. Results showed that Pb, Cd, Cu, Zn, Cr and Ni have accumulated in the river sediments after about 40 years of agricultural development, with average concentrations 1.23–1.71 times higher than local soil background values. Among them Ni, Cr and Cu were of special concern and they may pose adverse biological effects. By calculating enrichment factor (EF), it was found that the trace metal accumulation was still mainly ascribed to natural weathering processes, but anthropogenic contribution could represent up to 40.09% of total sediment content. For Pb, geochemical and isotopic approaches gave very similar anthropogenic contributions. Principal component analysis (PCA) further suggested that the anthropogenic Pb, Cu, Cr and Ni inputs were mostly related to the regional atmospheric deposition of industrial emissions and gasoline combustion, which had a strong affinity for iron oxides in the sediments. Concerning Cd, however, it mainly originated from local fertilizer applications and was controlled by sediment carbonates. - Graphical abstract: The trace metal accumulation was mainly ascribed to natural weathering processes, but anthropogenic contribution could represent up to 40.09% of total sediment content. Anthropogenic Pb, Cu, Cr and Ni mostly came from atmospheric deposition, while fertilizer application was the main anthropogenic source of Cd. - Highlights: • Trace metals have accumulated in the Naolihe sediments. • Natural weathering was still a major contributor to metal accumulation. • Anthropogenic Pb, Cu, Cr and Ni mostly came from atmospheric deposition. • Local fertilizer application was the main anthropogenic source of Cd
[en] Lake Qinghai in the Qinghai-Tibet plateau is the largest lake in China. This study firstly reported the geochemistry of Cd in the lake. Water samples were collected from Lake Qinghai (n = 69) and Buha River (n = 12), while sediment (n = 22) and topsoil (n = 45) samples were collected from the lake and around the lake area, respectively. In addition, pore water samples (n = 20) were separated from sediment samples. Water samples were analyzed for pH, K, Na, Ca, Mg, Cl, S, and Cd, while sediment and topsoil samples were analyzed for K, Na, Ca, Mg, Al, Fe, Mn, S, Sc, and Cd. The average concentration of Cd was 0.014 μg L−1 in the water of Lake Qinghai and 0.007 μg L−1 in the water of Buha River. However, the average concentration of Cd was 0.320 μg L−1 in the sediment pore water, much higher than that in the lake water and river water. Cadmium concentration in the lake water might be mainly controlled by salinity, while it in the pore water might be mainly controlled by carbonate minerals. Cadmium concentration in the river water might be controlled by alkalinity and pH. The average concentration of Cd in the sediment was 0.284 mg kg−1. The enrichment of Cd in the lake sediment was significantly higher than that in the topsoil around the lake. Anthropogenic atmospheric deposition of Cd did not led to the increase in dissolved Cd level in the lake water, but led to its enrichment in the lake sediment.
[en] We investigated changes in element content and distribution in soil profiles in a study designed to monitor the geochemical changes accruing in soil due to long-term secondary effluent recharge, and its impact on the sustainability of the Soil Aquifer Treatment (SAT) system. Since the initial elemental contents of the soils at the studied site were not available, we reconstructed them using scandium (Sc) as a conservative tracer. By using this approach, we were able to produce a mass-balance for 18 elements and evaluate the geochemical changes resulting from 19 years of effluent recharge. This approach also provides a better understanding of the role of soils as an adsorption filter for the heavy metals contained in the effluent. The soil mass balance suggests 19 years of effluent recharge cause for a significant enrichment in Cu, Cr, Ni, Zn, Mg, K, Na, S and P contents in the upper 4 m of the soil profile. Combining the elements lode record during the 19 years suggest that Cr, Ni, and P inputs may not reach the groundwater (20 m deep), whereas the other elements may. Conversely, we found that 58, 60, and 30% of the initial content of Mn, Ca and Co respectively leached from the upper 2-m of the soil profile. These high percentages of Mn and Ca depletion from the basin soils may reduce the soil's ability to buffer decreases in redox potential pe and pH, respectively, which could initiate a reduction in the soil's holding capacity for heavy metals. - Highlights: • Sc proved as a reliable tracer for reconstructing the initial soil elemental contents. • Mass-balance for 18 elements resulting from 19 years of SAT operation is presented. • After 19 years of operation Cr, Ni, and P inputs may not reach the groundwater. • The inputs of other 15 elements may reach the groundwater. • 58, 60, 30% of initial soil content of Mn, Ca, Co res. leached from the upper 2-m
[en] Eighteen polycyclic aromatic hydrocarbons (PAHs) were analyzed in 29 surface water, 29 suspended particulate matter (SPM), 28 sediment, and 10 pore water samples from Daliao River water system in dry season. The total PAH concentration ranged from 570.2 to 2318.6 ng L-1 in surface water, from 151.0 to 28483.8 ng L-1 in SPM, from 102.9 to 3419.2 ng g-1 in sediment and from 6.3 to 46.4 μg l-1 in pore water. The concentration of dissolved PAHs was higher than that of particulate PAHs at many sites, but the opposite results were generally observed at the sites of wastewater discharge. The soluble level of PAHs was much higher in the pore water than in the water column. Generally, the water column of the polluted branch streams contained higher content of PAHs than their mainstream. The environmental behaviors and fates of PAHs were examined according to some physicochemical parameters such as pH, organic carbon, SPM content, water content and grain size in sediments. Results showed that organic carbon was the primary factor controlling the distribution of the PAHs in the Daliao River water system. Partitioning of PAHs between sediment solid phase and pore water phase was studied, and the relationship between log Koc and log Kow of PAHs on some sediments and the predicted values was compared. PAHs other than naphthalene and acenaphthylene would be accumulated largely in the sediment of the Dalaio River water system. The sources of PAHs were evaluated employing ratios of specific PAHs compounds and different wastewater discharge sources, indicating that combustion was the main source of PAHs input.
[en] Vertical profiles of metals were measured by the in situ application of DGT (diffusive gradients in thin films). Well-defined laboratory systems ensured the good reproducibility and precision DGT accumulated metals on a chelex resin after diffusional transport through a layer of hydrogel. Three kinds of DGT probes (with three thicknesses of diffusive gel: 0.40 mm, 0.80 mm and 1.92 mm) measured interfacial concentration and induced flux from solid to solution phase which had intricate variations with depth. The DGT induced flux and interfacial concentration of four metals belonged to 'partially sustained' state, indicating a labile equilibrium of metals between solid phase and porewater. The concentration profiles showed the good correlation between Mn and Co and peak concentrations of Mn and Fe between -2.00 cm and -5.25 cm with depth. - Highlights: → Vertical profiles of four metals in sediments were measured by DGT. → The response of the DGT to deployment belongs to 'partially sustained' case. → Reproducibility and accuracy (±4%) ensured the good operation of DGT. → The fine distribution of the concentration of four metals was researched. → DGT was an efficient tool for the determination of metals in porewater. - Vertical profiles of metals were measured by the in situ application of DGT (diffusive gradients in thin films).
[en] In order to study element accumulation and trophic transfer in the food web, sixteen benthic invertebrate species and nine fish species were collected from the Daliao River estuary for analysis of toxic elements and nitrogen stable isotope in the muscle tissue. The concentrations ranged between 1.44–17.98, 0.01–9.30, 0.17–36.15, 0.7–145.4, 0.01–0.33, 0.14–14.88, 0.10–2.51, 0.02–0.14, and 19.3–221.1 mg kg−1 for As, Cd, Cu, Hg, Ni, Pb, Sb, and Zn, respectively. As, Cd, Cu, and Zn were significantly higher in the benthic invertebrates than in fish, whereas Hg and Sb were significantly lower. In addition, the benthic invertebrates were characterized by the highest bioaccumulation factor (BAF) for Cd, whereas the fish were characterized by the highest BAF for Hg. A significant decrease in Cd, Cr, Cu, and Ni levels, and a significant increase in Hg and Sb levels were observed with increasing trophic levels. - Highlights: • Toxic elements and trophic level were determined in biota from Daliao River estuary. • Benthic invertebrates had higher As, Cd, Cu, Zn and lower Hg and Sb levels than fish. • Benthic invertebrates accumulated high As levels, while fish accumulated high Hg levels. • Cd, Cr, Cu, Ni levels decreased, and Hg and Sb levels increased with trophic levels.
[en] Highlights: • S(IV)/PDS system showed synergistic degradation of BPA than S(IV) and PDS. • BPA degradation involved hydroxyl and oxysulfur radicals in the S(IV)/PDS system. • Based on the identified intermediates, the BPA degradation pathway was proposed. - Abstract: In this study, the bisulfite-peroxydisulfate system (S(IV)/PDS) widely used in polymerization was innovatively applied for organic contaminants degradation in water. The addition of S(IV) into PDS system remarkably enhanced the degradation efficiency of bisphenol A (BPA, a frequently detected endocrine disrupting chemical in the environments) from 17.0% to 84.7% within 360 min. The degradation efficiency of BPA in the S(IV)/PDS system followed pseudo-first-order kinetics, with rate constant values ranging from 0.00005 min"−"1 to 0.02717 min"−"1 depending on the operating parameters, such as the initial S(IV) and PDS dosage, solution pH, reaction temperature, chloride and water type. Furthermore, nitrogen purging experiment, radical scavenging experiment and electron spin resonance (ESR) analysis were used to elucidate the possible mechanism. The results revealed that sulfate radical was the dominant reactive species in the S(IV)/PDS system. Finally, based on the results of liquid chromatography–mass spectrometry (LC–MS) and gas chromatography–mass spectrometry (GC–MS), the BPA degradation pathway was proposed to involve β-scission (C−C), hydroxylation, dehydration, oxidative skeletal rearrangement, and ring opening. This study helps to characterize the combination of PDS and inorganic S(IV), a common industrial contaminant, to generate reactive species to enhance organic contaminants degradation in water.
[en] A random sample of pairs of animal feeds and manures were collected from 215 animal barns in Beijing and Fuxin regions of China. The concentrations of Cd in manures and feeds ranged from non-detectable to 129.8 mg/kg dry weight and non-detectable to 31 mg/kg dry weight, respectively. The concentrations of Cd in pig, dairy cow and chicken manures were positively correlated to those in their feeds. About 30% of the manure samples contained Cd concentrations higher than the upper limit for use in farmlands, and pig and chicken manures might be the primary contributors of Cd to farmlands. The farmlands in Beijing and around the Fuxin Downtown areas would exceed the soil quality criteria within several decades according to current manure Cd loading rates. Undoubtedly, more scientific animal production and manure management practices to minimize soil pollution risks are necessary for the two regions.