Leaching of hydrophobic Cu and Zn from discarded marine antifouling paint residues: Evidence for transchelation of metal pyrithiones

Leaching of Cu and Zn from a composite of discarded antifouling paint residues ([Cu] = 288 mg g⁻¹; [Zn] = 96 mg g⁻¹) into natural sea water has been studied over a period of 75 h. Total Cu and Zn were released according to a pseudo first-order reaction, with rate constants on the order of 0.3 and 2.5 (mg L⁻¹)⁻¹ h⁻¹, respectively, and final concentrations equivalent to the dissolution of about 8 and 2% of respective concentrations in the composite. Time-distributions of hydrophobic metals, determined by solid phase extraction-methanol elution, were more complex. Net release of hydrophobic Cu was greater in the absence of light than under a sequence of light-dark cycles; however, hydrophobic Zn release was not detected under the former conditions but contributed up to 50% of total aqueous Zn when light was present. These observations are interpreted in terms of the relative thermodynamic and photolytic stabilities of biocidal pyrithione complexes.     

Surfactant-soil interactions during surfactant-amended remediation of contaminated soils by hydrophobic organic compounds: a review

Surfactants are amphiphilic molecules that reduce aqueous surface tension and increase the solubility of hydrophobic organic compounds (HOCs). Surfactant-amended remediation of HOC-contaminated soils and aquifers has received significant attention as an effective treatment strategy - similar in concept to using soaps and detergents as washing agents to remove grease from soiled fabrics. The proposed mechanisms involved in surfactant-amended remediation include: lowering of interfacial tension, surfactant solubilization of HOCs, and the phase transfer of HOC from soil-sorbed to pseudo-aqueous phase. However, as with any proposed chemical countermeasures, there is a concern regarding the fate of the added surfactant. This review summarizes the current state of knowledge regarding nonionic micelle-forming surfactant sorption onto soil, and serves as an introduction to research on that topic. Surfactant sorption onto soil appears to increase with increasing surfactant concentration until the onset of micellization. Sorbed-phase surfactant may account for the majority of added surfactant in surfactant-amended remediation applications, and this may result in increased HOC partitioning onto soil until HOC solubilization by micellar phase surfactant successfully competes with increased HOC sorption on surfactant-modified soil. This review provides discussion of equilibrium partitioning theory to account for the distribution of HOCs between soil, aqueous phase, sorbed surfactant, and micellar surfactant phases, as well as recently developed models for surfactant sorption onto soil. HOC partitioning is characterized by apparent soil-water distribution coefficients in the presence of surfactant.     

Investigation of potential interferences on the measurement of dissolved reactive phosphate using zirconium oxide-based DGT technique

A diffusive gradients in thin films (DGT) technique based on hydrous zirconium oxide (Zr-oxide) has been recently developed for the measurement of dissolved reactive phosphate (DRP). In this study, the detailed performance of the DGT technique is reported. Spiking experiments revealed that several orthophosphate monoester compounds contributed to the Zr-oxide DGT measurements of DRP. However, such a phenomenon is unlikely to occur during field conditions due to the low concentration of organic P in typical natural waters. The presence of Cl- (up to 106 g/L), SO42- (up to 16 g/L), HCO3- (up to 817 g/L), and AsO2- and AsO 3 4 (both up to 1 mg As/L) in solutions had negligible effects on the measurement of DRP. The threshold concentrations of Cl-, SO42- and HCO3- have been increased from previous reports for the measurements of DRP using other adsorbent-based DGT techniques. The capacity for DGT measurements of DRP decreased with increasing solution pH (4.2-9.2). The lowest capacity (95 μg P/m2 at pH 9.2) was still greater than that of other DGT techniques that are usually used for the measurement of DRP (2-12 μg P/cm2 ). The Zr-oxide binding gel could be stored for up to 2 years without any aging effect. This period of validity was considerably longer than the ferrihydrite binding gel that is commonly used in present DGT devices (6 months). The field application revealed that the concentrations of DRP measured in three fresh water samples using the Zr-oxide DGT technique were in agreement with those of the traditional colorimetric method.     

湖泊疏浚对沉积物再悬浮及磷迁移影响的模拟研究

选择太湖梅梁湾污染沉积物为研究对象,选取夏季和冬季两个典型季节,进行室内模拟试验研究了湖泊疏浚对沉积物再悬浮及磷迁移的影响.结果表明,研究区模拟疏浚20 cm能够有效地抑制沉积物发生再悬浮,冬季疏浚比夏季疏浚抑制效果更好,在扰动过程中夏季未疏浚对照和疏浚水柱总悬浮物(TSS)最大含量分别为初始值的7.0和2.2倍;而冬季未疏浚对照和疏浚水柱分别为24.3和6.4倍.统计分析发现,夏、冬两季模拟试验未疏浚对照和疏浚水柱中总磷(TP)、磷酸盐(PO34--P)含量都与TSS含量变化呈现显著正相关(P<0.05),表明风浪扰动造成大量沉积物再悬浮,并伴随内源磷的释放是水柱中TP和磷酸盐的主要来源.夏季模拟试验疏浚对水柱中TP和磷酸盐负荷控制效果略差,冬季模拟试验疏浚水柱中TP和磷酸盐含量都显著(P<0.01)低于未疏浚对照.利用薄膜扩散梯度(DGT)技术研究了夏季疏浚沉积物-水界面上间隙水中溶解态活性磷(DRP)垂向分布,未疏浚水土界面中间隙水DRP扩散层厚度大于疏浚样,但疏浚样间隙水DRP在水土界面的离子浓度势能大于未疏浚对照样,表明底泥疏浚可以有效地降低疏浚区间隙水中DRP潜在的释放风险,但水动力作用下短期内可能会导致疏浚间隙水中DRP释放.对于太湖这样的大型浅水湖泊,确定最佳的疏浚时令、疏浚深度及疏浚范围至关重要.     

基于梯度薄膜扩散技术评估黑麦草吸收Cd的研究

分别采用固态结合相(Chelex100)和液态结合相(聚丙烯酸钠,PAAS)的梯度薄膜扩散技术(DGT)对盆栽黑麦草实验中的土壤有效态Cd进行了提取,结果表明2种不同结合相的DGT技术提取的土壤有效态Cd含量与黑麦草地上部和地下部的Cd含量都呈显著相关关系,其相关系数分别为0.90,0.89(Chelex100-DGT)和0.90,0.87(PAAS-DGT).运用多元统计分析方法研究土壤pH值、阳离子交换量(CEC)、有机质(OM)和土壤颗粒组成等理化指标的影响,提取出2种主成分因子,建立逐步回归模型.第1主成分与OM和黏粒组成之间呈显著相关,定义为代表土壤中影响重金属生物有效性的“有机指标”,第2主成分则土壤pH值和CEC相关程度较高,定义为代表土壤中影响重金属生物有效性的“无机指标”.研究表明Chelex100-DGT和PAAS-DGT技术均能较好预测黑麦草对Cd的吸收,且包含了土壤理化性质的影响.     

Determining cadmium bioavailability in sediment profiles using diffusive gradients in thin films

Cadmium(Cd) uptake by plants or benthic organisms largely depends on its bioavailability in sediments,so it is necessary to understand Cd bio availability for determining its ecological risks in riverine sediments.Pore water is easily disturbed during sample collection,indicating that there was a shortage of traditional methods for investigating Cd bio availability.Here,sediment cores were collected from rivers,after which sequential extraction and diffusive gradients in thin films(DGT) method were employed to determine Cd potential bio availability in the sediments and pore water.We found that Cd concentrations measured by DGT were lower than that in pore water profiles,and Cd distribution in various fractions changed remarkably.Pearson correlation analysis showed significant positive correlations between Cd concentrations measured by DGT and total Cd concentrations(r~2=0.76),exchangeable and weak acid soluble fraction(r~2=0.68),ferromanganese fraction(r~2=0.72) and bound organic matter or oxidizable fraction(r~2=0.54).However,the correlation was relatively low between Cd concentrations measured by DGT and that in pore water profiles(r~2=0.26).These results demonstrated that DGT method could provide more accurate information of Cd bio availability in sediment profiles than traditional methods.     

Mobility and sulfidization of heavy metals in sediments of a shallow eutrophic lake, Lake Taihu, China

The technique of DGT (diffusive gradients in thin films) using three diffusive gel thicknesses was applied to estimate the mobility and bioavailability of heavy metals in sediments and porewater of Lake Taihu, China. The DGT results showed significantly positive correlations between Co, Pb, Cd and Mn, and Ni and Fe concentrations in porewater. Cu and Zn showed a significantly negative correlation with Mn, due to Cu combination with carbonates and Zn derived from agricultural pollution, respectively. The rank order of average concentrations of Co, Ni and Cd at each station was DGT_1.92 >DGT_0.78 >DGT_0.39, suggesting stronger resupply from sediments to porewater when using thicker diffusive gels. Comparing centrifugation and DGT measurements, Co, Ni and Cd are highly labile; Mn and Fe are moderately labile; and Cu, Zn and Pb are slightly labile. The variations of AVS concentrations in sediment cores indicate that metal sulfides in deeper layers are easily diffused into surface sediments.     

薄膜干燥法再生聚苯乙烯树脂的研究

利用溶剂溶解回收的聚苯乙烯塑料,将其涂布于不锈钢传送带上,以水蒸气为加热介质,经薄膜干燥法获得再生聚苯乙烯树脂.再生的聚苯乙烯树脂性能优异,溶剂回收率达97%以上.     

Extruded Cornstarch-Glycerol-Polyvinyl Alcohol Blends: Mechanical Properties, Morphology, and Biodegradability

Elongation properties of extruded cornstarch were improved by blending with glycerol. Further blending of starch-glycerol with polyvinyl alcohol (PVOH) resulted in significant improvements in both tensile strength (TS) and elongation at break. Samples of starch-glycerol without PVOH equilibrated at 50% relative humidity had a TS of 1.8 MPa and elongation of 113%, whereas those containing PVOH had a TS and elongation of 4 MPa and 150%, respectively. Dynamic mechanical analysis (DMA) of starch-glycerol-PVOH blends showed that decreases in glass transition temperatures (T _g values) were proportional to glycerol content. Scanning electron microscopy (SEM) of fractured surfaces revealed numerous cracks in starch-glycerol (80:20) samples. Cracks were absent in starch-glycerol (70:30) samples. In both blends, many starch granules were exposed at the surface. No exposed starch granules were visible in blends with added PVOH. Starch-glycerol samples incubated in compost lost up to 70% of their dry weight within 22 days. Addition of PVOH lowered both the rate and extent of biodegradation.