不同添加剂对铅冶炼污染石灰性土壤的修复及土壤性质的影响研究

探讨了污水处理厂脱水污泥、枯草和磷矿粉对受铅冶炼污染的石灰性土壤(全Pb、Cd、Zn含量分别为2337、21.4、486 mg·kg-1,DTPA提取态Pb、Cd、Zn含量分别为1035、14.5、68.7 mg·kg-1)中重金属的稳定效果及对土壤性质的影响.其中,污泥和枯草均按200 g·kg-1(干重)的用量施用,磷矿粉按n(P)∶n(Pb)=2∶1比例施用,培养80 d.研究结果表明,单独施用污泥可使土壤DTPA-Pb含量降低18.0%(p0.05),并可显著降低土壤pH,增加土壤氮、磷有效性和电导率、DTPA-Cd、DTPA-Zn含量,其中,DTPA-Cd、DTPA-Zn含量增加比例均达到10%以上.单独施用枯草可使土壤DTPA-Pb含量降低10.7%(p0.05),土壤有机质含量增加26.4%(p0.05),对土壤其它性状影响较小.磷矿粉单独施用时对土壤性质影响较小.与污泥单独施用相比,磷矿粉与污泥配合施用时,可使土壤DTPA-Cd含量降低11.9%.     

钙、氯对磷酸盐稳定污染土壤中铅的促进作用研究

为探讨促进磷酸盐稳定污染土壤中铅的方法,在全铅含量为517 mg·kg-1的铅冶炼污染土壤中加入5 mmol·kg-1磷酸盐,同时加入10mmol·kg-1硝酸钙或5 mmol·kg-1氯化钾,在15%或30%的含水率下培养40 d,之后种植黑麦草.结果表明,与单独施用磷酸盐相比,采用磷酸盐与钙、氯结合或增加培养期间的土壤含水率后,土壤DTPA-Pb含量下降3.92%~26.1%;对于同一添加剂处理,培养期间土壤含水率从15%增加到30%,土壤有效铅(DTPA-Pb)含量下降8.83%~24.4%.增加土壤含水率后,土壤有效磷(Olsen-P)含量均显著升高(p0.05).土壤铅的EXAFS分析表明,与未施用磷酸盐的对照相比,土壤中加入磷酸盐后矿物态铅的比例由57%上升至81%,加施钙、氯或增加土壤含水率后,多数处理矿物态铅的比例有所下降,而有机结合态铅比例上升.与对照相比,污染土壤中施用磷酸盐后,植物产量大幅增加,但施用钙、氯或增加培养期间含水率后,部分处理植物产量有所下降.以上结果表明,在铅冶炼污染土壤中加入磷酸盐时,加入钙、氯或者增加土壤含水率均有利于铅的稳定,但以上措施可能对植物生长产生不利影响.     

Spectroscopic speciation and quantification of lead in phosphate-amended soils

The immobilization of Pb in contaminated soils as pyromorphite [Pb(5)(PO(4))(3)Cl, OH, F] through the addition of various phosphate amendments has gained much attention in the remediation community. However, it is difficult to fully determine the speciation and amount of soil Pb converted to pyromorphite by previously employed methods, such as selective sequential extraction procedures and scanning electron microscopy coupled with energy dispersive X-ray spectroscopy, which often lead to erroneous results in these non-equilibrated and heterogeneous systems. Statistical analysis by linear combination fitting (LCF) applied to X-ray absorption fine structure (XAFS) spectroscopic data of Pb-contaminated soil samples relative to known Pb reference material provides direct, in situ evidence of dominate Pb species in the amended soils without chemical or physical disruption to the Pb species as well as a weighted quantification output. The LCF-XAFS approach illustrated that pyromorphite concentration ranged from 0% (control soil) to 45% (1% phosphoric acid amendment, residence time of 32 mo) relative to the total Pb concentration. The Pb speciation in the nonamended control soil included Pb-sulfur species (galena + angelsite = 53%), adsorbed Pb (inner-sphere + outer-sphere + organic-bound = 45%), and Pb-carbonate phases (cerussite + hydrocerussite = 2%). The addition of P promoted pyromorphite formation and the rate of formation increased with increasing P concentration (up to 45%). The supplemental addition of an iron amendment as an iron-rich byproduct with triple superphosphate (TSP) enhanced pyromorphite formation relative to independent TSP amendment of like concentrations (41 versus 29%). However, the amendment of biosolids and biosolids plus TSP observed little pyromorphite formation (1-16% of total Pb), but a significant increase of sorbed Pb was determined by LCF-XAFS.     

micro-XANES and micro-XRF investigations of metal binding mechanisms in biosolids

Micro-X-ray fluorescence (micro-XRF) microprobe analysis and micro-X-ray absorption near-edge structure (micro-XANES) spectroscopy were employed to identify Fe and Mn phases and their association with selected metals in two biosolids (limed composted [LC] and Nu-Earth) before and after treatment to remove organic carbon (OC). Spatial correlations derived from elemental mapping of XRF images showed strong correlations between Fe and Cd, Cr, Pb, or Zn (r2= 0.65-0.92) before and after removal of most of the OC. The strong correlation between Fe and Cu that was present in intact samples disappeared after OC removal, suggesting that Cu was associated with OC coatings that may have been present on Fe compounds. Except for Fe and Cr, the spatial correlations of metals with Mn were improved after treatment to remove OC, indicating that the treatment may have altered more than the OC in the system. The Fe micro-XANES spectra of the intact biosolids sample showed that every point had varying mixtures of Fe(II and III) species and no two points were identical. The lack of uniformity in Fe species in the biosolids sample illustrates the complexity of the materials and the difficulty of studying biosolids using conventional analytical tools or chemical extraction techniques. Still, these microscopic observations provide independent information supporting the previous laboratory and field hypothesis that Fe compounds play a major role in retention of environmentally important trace elements in biosolids. This could be due to co-precipitation of the metals with Fe, adsorption of metals by Fe compounds, or a combination of both mechanisms.     

The distribution, solid-phase speciation, and desorption/dissolution of As in waste iron-based drinking water treatment residuals

Arsenic concentrations and solid-phase speciation were assessed as a function of depth through Fe-media beds for two commercially available products (Granular Ferric Hydroxide-GFH and Bayoxide E33-E33) from pilot-scale water treatment field tests. These results were compared with data from solution (de-ionized water-DI-H2O) concentrations of As equilibrated with Fe-media in an anoxic environment at 4 degrees C. The materials had a high capacity for As (GFH media 9620 mg kg(-1) As, E33 Media 5246 mg kg(-1)). Arsenic concentrations decreased with bed depth. For E33, X-ray absorption near-edge spectroscopy results showed that As(V) was the dominant solid-phase species. For GFH, As(III) was detected and the proportion (relative to As(V)) of As(III) increased with bed depth. Arsenic concentrations in DI-H2O equilibrated with the media were low (35 microg l(-1)) over a period of 50 d. Arsenic concentrations in the equilibrated solutions also decreased with depth. Results from tests on soluble As speciation show that As in solution is in the form of As(V). Kinetic desorption experiments carried out at different pH values (3, 5, 7, 8, and 9) show that the media exhibit some acid/base neutralization capacity and tend to bind As sufficiently. Concentrations of As in the pH desorption experiments were in the same order of magnitude as the toxicity characteristic leaching procedure extractions (tens of microgl(-1)) except at low pH values. For the GFH media tested at a pH of three, As increases in solution and is mainly associated with colloidal (operationally defined as between 0.1 and 1.0 microm) iron.     

Advanced in situ spectroscopic techniques and their applications in environmental biogeochemistry: introduction to the special section

Understanding the molecular-scale complexities and interplay of chemical and biological processes of contaminants at solid, liquid, and gas interfaces is a fundamental and crucial element to enhance our understanding of anthropogenic environmental impacts. The ability to describe the complexity of environmental biogeochemical reaction mechanisms relies on our analytical ability through the application and developmemnt of advanced spectroscopic techniques. Accompanying this introductory article are nine papers that either review advanced in situ spectroscopic methods or present original research utilizing these techniques. This collection of articles summarizes the challenges facing environmental biogeochemistry, highlights the recent advances and scientific gaps, and provides an outlook into future research that may benefit from the use of in situ spectroscopic approaches. The use of synchrotron-based techniques and other methods are discussed in detail, as is the importance to integrate multiple analytical approaches to confirm results of complementary procedures or to fill data gaps. We also argue that future direction in research will be driven, in addition to recent analytical developments, by emerging factors such as the need for risk assessment of new materials (i.e., nanotechnologies) and the realization that biogeochemical processes need to be investigated in situ under environmentally relevant conditions.     

In vitro and in vivo approaches for the measurement of oral bioavailability of lead (Pb) in contaminated soils: a review

We reviewed the published evidence of lead (Pb) contamination of urban soils, soil Pb risk to children through hand-to-mouth activity, reduction of soil Pb bioavailability due to soil amendments, and methods to assess bioaccessibility which correlate with bioavailability of soil Pb. Feeding tests have shown that urban soils may have much lower Pb bioavailability than previously assumed. Hence bioavailability of soil Pb is the important measure for protection of public health, not total soil Pb. Chemical extraction tests (Pb bioaccessibility) have been developed which are well correlated with the results of bioavailability tests; application of these tests can save money and time compared with feeding tests. Recent findings have revealed that fractional bioaccessibility (bioaccessible compared to total) of Pb in urban soils is only 5-10% of total soil Pb, far lower than the 60% as bioavailable as food-Pb presumed by U.S.-EPA (30% absolute bioavailability used in IEUBK model).     

添加剂对伴矿景天修复石灰性铅冶炼污染土壤的影响

为了探讨利用伴矿景天(Sedum plumbizincicola)修复北方重金属污染土壤的可行性,在河南省某铅冶炼形成的污染农田(全镉、铅和锌含量分别为2.65、261和130 mg·kg-1)上种植种子苗或扦插苗伴矿景天,并设对照(CK)、单独尿素(U)、尿素和单质硫(U+S)、尿素与鸡粪(U+CM)配合处理,生长7个月后采样分析.结果表明,种子苗产量比扦插苗高45.8%~162.0%,U、U+CM处理产量均明显高于CK,而U+S处理产量有所下降.种子苗地上部镉含量比扦插苗高15%~99%(p0.05),多数处理铅和锌含量也是种子苗高于扦插苗.与CK相比,各处理措施均导致伴矿景天地上部镉和铅含量下降,而U+S、U+CM处理均导致伴矿景天地上部锌含量上升.从伴矿景天地上部重金属积累量判断,与CK相比,对于镉,仅种子苗U+CM处理镉积累量有所上升;U处理种子苗和扦插苗地上部锌积累量分别比CK上升43.5%和32.3%,两种苗U+S处理锌积累量比CK分别上升11.1%和22.3%.种子苗和扦插苗地上部镉的积累量分别为137~178 g·hm-2和43.7~64.8 g·hm-2,锌的积累量分别为297~1042 g·hm-2和162~326 g·hm-2,两类苗对铅的积累量小于28.8 g·hm-2.U+CM处理对伴矿景天地上部锌吸收的促进作用主要是由于鸡粪中含有大量的有效锌.以上结果表明,可利用种子苗伴矿景天结合尿素的施用对铅冶炼污染石灰性土壤进行修复.     

Bioaccessibility of lead sequestered to corundum and ferrihydrite in a simulated gastrointestinal system

Lead (Pb) sorption onto oxide surfaces in soils may strongly influence the risk posed from incidental ingestion of Pb-contaminated soil. Lead was sorbed to model oxide minerals of corundum (alpha-Al(2)O(3)) and ferrihydrite (Fe(5)HO(8).4H(2)O). The Pb-sorbed minerals were placed in a simulated gastrointestinal tract (in vitro) to simulate ingestion of Pb-contaminated soil. The changes in Pb speciation were determined using extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge spectroscopy (XANES). Both corundum (sorption maximum of 2.13 g kg(-1)) and ferrihydrite (sorption maximum of 38.6 g kg(-1)) have been shown to sorb Pb, with ferrihydrite having a very high affinity for Pb. The gastric bioaccessible Pb for corundum was >85% for corundum when the concentration of Pb was >200 mg kg(-1). Bioaccessible Pb was not detectable at 4. However, much of the sorbed Pb will become bioaccessible under gastric conditions (pH 1.5-2.5) if this soil is ingested. Caution should be used before using these materials to remediate a soil where soil ingestion is an important exposure pathway.