The SDS22:PP1:I3 complex: SDS22 binding to PP1 loosens the active site metal to prime metal exchange.

SDS22 and Inhibitor-3 (I3) are two ancient regulators of protein phosphatase 1 (PP1) that regulate multiple essential biological processes. Both SDS22 and I3 form stable dimeric complexes with PP1; however, and atypically for PP1 regulators, they also form a triple complex, where both proteins bind to PP1 simultaneously (SPI complex). Here we report the crystal structure of the SPI complex. While both regulators bind PP1 in conformations identical to those observed in their individual PP1 complexes, PP1 adopts the SDS22-bound conformation, which lacks its M1 metal. Unexpectedly, surface plasmon resonance (SPR) revealed that the affinity of I3 for the SDS22:PP1 complex is ∼10-fold lower than PP1 alone. We show that this change in binding affinity is solely due to the interaction of I3 with the PP1 active site, specifically PP1's M2 metal, demonstrating that SDS22 likely allows for PP1 M2 metal exchange and thus PP1 biogenesis.

Hair geochemical composition of children from Vilnius kindergartens as an indicator of environmental conditions.

The research is based on analysis data of Cr, Cu, Mn, Ni, V, Zn (metals) and S in the hair of 47 girls and 63 boys from eight Vilnius kindergartens and the distribution pattern of high metal concentrations and bioavailability in snow-cover dust, also dust samples from vents of characteristic pollution sources. The kindergartens were selected according to topsoil total contamination index and dust-related indices. Significantly higher Cu, Mn, Ni and Zn concentrations in the hair of girls (means are 1.1, 1.9, 1.3, 1.2 times higher) and the differences between hair of genders according to inter-element correlation and clustering were found. Analysis of Spearman correlation coefficients between metal concentrations in hair of each gender and dust metal concentrations or metal loading rates at their residence sites revealed that for Mn, Cu and Zn, they are insignificant, while for Cr, Ni, Pb and V, they are mainly significant positive (except V in female hair). The correlation of the contents of Cr, Ni and V in dust with respective concentrations in hair was more significant for boys (p < 0.001) than for girls. Only a few cases with a significant Cr, Ni, Cu, Pb and Zn increase were revealed in hair of children attending polluted kindergartens in comparison with control. It was concluded that relationship between metal concentrations in hair and dust-related indices is more expressed for children's residence sites than for their kindergarten sites. The gender-based grouping and site-by-site study design are recommended in the studies of reflection of environmental exposure in hair.

Sophisticated Design of Covalent Organic Frameworks with Controllable Bimetallic Docking for a Cascade Reaction.

Precise control of the number and position of the catalytic metal ions in heterogeneous catalysts remains a big challenge. Here we synthesized a series of two-dimensional (2D) covalent organic frameworks (COFs) containing two different types of nitrogen ligands, namely imine and bipyridine, with controllable contents. For the first time, the selective coordination of the two nitrogen ligands of the 2D COFs to two different metal complexes, chloro(1,5-cyclooctadiene)rhodium(I) (Rh(COD)Cl) and palladium(II) acetate (Pd(OAc)2 ), has been realized using a programmed synthetic procedure. The bimetallically docked COFs showed excellent catalytic activity in a one-pot addition-oxidation cascade reaction. The high surface area, controllable metal-loading content, and predesigned active sites make them ideal candidates for their use as heterogeneous catalysts in a wide range of chemical reactions.

Detection of metallic cobalt and chromium liver deposition following failed hip replacement using T2* and R2 magnetic resonance.

BACKGROUND: Failed hip prostheses can cause elevated circulating cobalt and chromium levels, with rare reports of fatal systemic organ deposition, including cobalt cardiomyopathy. Although blood cobalt and chromium levels are easily measured, organ deposition is difficult to detect without invasive biopsy. The T2* magnetic resonance (MR) method is used to quantify tissue iron deposition, and plays an important role in the management of iron-loading conditions. Cobalt and chromium, like iron, also affect magnetism and are proposed MR contrast agents. CASE PRESENTATION: We describe a case of a 44-year-old male with a failed hip implant and very elevated blood cobalt and chromium levels. Despite normal cardiac MR findings, liver T2* and R2 values were abnormal, triggering tissue biopsy. Liver tissue analysis, including X-ray fluorescence, demonstrated heavy elemental cobalt and chromium deposition in macrophages, and no detectable iron. CONCLUSIONS: Our case demonstrates T2* and R2 quantification of liver metal deposition in a patient with a failed hip implant. Further work is needed to investigate the role of T2* and R2 MR in the detection of metal deposition from metal on metal hip prostheses.

Large-Scale Synthesis of High-Loading Single Metallic Atom Catalysts by a Metal Coordination Route.

Single atom catalyst (SAC) is one of the most efficient and versatile catalysts with well-defined active sites. However, its facile and large-scale preparation, the prerequisite of industrial applications, has been very challenging. This dilemma originates from the Gibbs-Thomson effect, which renders it rather difficult to achieve high single atom loading (< 3 mol%). Further, most synthesizing procedures are quite complex, resulting in significant mass loss and thus low yields. Herein, a novel metal coordination route is developed to address these issues simultaneously, which is realized owing to the rapid complexation between ligands (e.g., biuret) and metal ions in aqueous solutions and subsequent in situ polymerization of the formed complexes to yield SACs. The whole preparation process involves only one heating step operated in air without any special protecting atmospheres, showing general applicability for diverse transition metals. Take Cu SAC for an example, a record yield of up to 3.565 kg in one pot and an ultrahigh metal loading 16.03 mol% on carbon nitride (Cu/CN) are approached. The as-prepared SACs are demonstrated to possess high activity, outstanding selectivity, and robust cyclicity for CO2 photoreduction to HCOOH. This research explores a robust route toward cost-effective, massive production of SACs for potential industrial applications.

Emerging Strategies for the Synthesis of Correlated Single Atom Catalysts.

People have been looking for an energy-efficient and sustainable method to produce future chemicals for decades. Heterogeneous single-atom catalysts (SACs) with atomic dispersion of robust, well-characterized active centers are highly desirable. In particular, correlated SACs with cooperative interaction between adjacent single atoms allow the switching of the single-site pathway to the dual or multisite pathway, thus promoting bimolecular or more complex reactions for the synthesis of fine chemicals. Herein, the structural uniqueness of correlated SACs, including the intermetal distance and electronic interaction in homo/heteronuclear metal sites is featured. Recent advances in the production methods of correlated SACs, showcasing the research status and challenges in traditional methods (such as pyrolysis, wet impregnation, and confined synthesis) for building a comprehensive multimetallic SAC library, are summarized. Emerging strategies such as process automation and continuous-flow synthesis are highlighted, minimizing the inconsistency in laboratory batch production and allowing high throughput screening and upscaling toward the next-stage chemical production by correlated SACs.

MnO2-Ir Nanowires: Combining Ultrasmall Nanoparticle Sizes, O-Vacancies, and Low Noble-Metal Loading with Improved Activities towards the Oxygen Reduction Reaction.

Although clean energy generation utilizing the Oxygen Reduction Reaction (ORR) can be considered a promising strategy, this approach remains challenging by the dependence on high loadings of noble metals, mainly Platinum (Pt). Therefore, efforts have been directed to develop new and efficient electrocatalysts that could decrease the Pt content (e.g., by nanotechnology tools or alloying) or replace them completely in these systems. The present investigation shows that high catalytic activity can be reached towards the ORR by employing 1.8 ± 0.7 nm Ir nanoparticles (NPs) deposited onto MnO2 nanowires surface under low Ir loadings (1.2 wt.%). Interestingly, we observed that the MnO2-Ir nanohybrid presented high catalytic activity for the ORR close to commercial Pt/C (20.0 wt.% of Pt), indicating that it could obtain efficient performance using a simple synthetic procedure. The MnO2-Ir electrocatalyst also showed improved stability relative to commercial Pt/C, in which only a slight activity loss was observed after 50 reaction cycles. Considering our findings, the superior performance delivered by the MnO2-Ir nanohybrid may be related to (i) the significant concentration of reduced Mn3+ species, leading to increased concentration of oxygen vacancies at its surface; (ii) the presence of strong metal-support interactions (SMSI), in which the electronic effect between MnOx and Ir may enhance the ORR process; and (iii) the unique structure comprised by Ir ultrasmall sizes at the nanowire surface that enable the exposure of high energy surface/facets, high surface-to-volume ratios, and their uniform dispersion.

Estimating metal loading into the sea from tidal rivers using total suspended solids and water quality models.

Metals are mainly transported with suspended sediments in tidal rivers, and it is difficult to describe the transformation process of metals. Freely dissolved metals and suspended metals (including acid-soluble, reducible, oxidizable, and residual metals) were separately analyzed according to a sequential extraction scheme. The regression of the observed suspended metals and total suspended solids (TSS) concentrations allowed us to couple the two pollutant types. TSS is a highly dynamic parameter, and a model can be developed to simulate TSS transport. Thus, a method including the following five steps was proposed to estimate the loadings of metals entering the sea using TSS concentrations and water quality models: (1) collecting and observing basic information on the hydrological conditions, pollution sources, and water quality of the studied river; (2) obtaining a regression model between the suspended metals and TSS and analyzing the potential of establishing a suspended metal flux model; (3) introducing a model describing the fluxes of water-soluble metals into the sea; (4) establishing a calculation model to determine the fluxes of suspended metals into the sea; and (5) characterizing the fluxes of metals into the sea. The method was programmed, and metal concentrations and fluxes could be characterized quickly when the basic river data were sufficient. In addition, if regional development scenarios could be set, metal loadings in all scenarios could be predicted through the procedure developed herein, and some effective suggestions on regional sustainable development might be proposed for decision makers. Integr Environ Assess Manag 2022;18:198-208. © 2021 SETAC.

Atomically dispersed Ir/α-MoC catalyst with high metal loading and thermal stability for water-promoted hydrogenation reaction.

Synthesis of atomically dispersed catalysts with high metal loading and thermal stability is challenging but particularly valuable for industrial application in heterogeneous catalysis. Here, we report a facile synthesis of a thermally stable atomically dispersed Ir/α-MoC catalyst with metal loading as high as 4 wt%, an unusually high value for carbide supported metal catalysts. The strong interaction between Ir and the α-MoC substrate enables high dispersion of Ir on the α-MoC surface, and modulates the electronic structure of the supported Ir species. Using quinoline hydrogenation as a model reaction, we demonstrate that this atomically dispersed Ir/α-MoC catalyst exhibits remarkable reactivity, selectivity and stability, for which the presence of high-density isolated Ir atoms is the key to achieving high metal-normalized activity and mass-specific activity. We also show that the water-promoted quinoline hydrogenation mechanism is preferred over the Ir/α-MoC, and contributes to high selectivity towards 1,2,3,4-tetrahydroquinoline. The present work demonstrates a new strategy in constructing a high-loading atomically dispersed catalyst for the hydrogenation reaction.

Liquid Phase Infiltration of Block Copolymers.

Novel materials with defined composition and structures at the nanoscale are increasingly desired in several research fields spanning a wide range of applications. The development of new approaches of synthesis that provide such control is therefore required in order to relate the material properties to its functionalities. Self-assembling materials such as block copolymers (BCPs), in combination with liquid phase infiltration (LPI) processes, represent an ideal strategy for the synthesis of inorganic materials into even more complex and functional features. This review provides an overview of the mechanism involved in the LPI, outlining the role of the different polymer infiltration parameters on the resulting material properties. We report newly developed methodologies that extend the LPI to the realisation of multicomponent and 3D inorganic nanostructures. Finally, the recently reported implementation of LPI into different applications such as photonics, plasmonics and electronics are highlighted.

Rational Design and Characterisation of Novel Mono- and Bimetallic Antibacterial Linde Type A Zeolite Materials.

The development of antimicrobial devices and surfaces requires the setup of suitable materials, able to store and release active principles. In this context, zeolites, which are microporous aluminosilicate minerals, hold great promise, since they are able to serve as a reservoir for metal-ions with antimicrobial properties. Here, we report on the preparation of Linde Type A zeolites, partially exchanged with combinations of metal-ions (Ag+, Cu2+, Zn2+) at different loadings (0.1-11.9 wt.%). We combine X-ray fluorescence, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray diffraction to monitor the metal-ion contents, distribution, and conservation of the zeolite structure after exchange. Then, we evaluate their antimicrobial activity, using agar dilution and optical-density monitoring of Escherichia coli cultures. The results indicate that silver-loaded materials are at least 70-fold more active than the copper-, zinc-, and non-exchanged ones. Moreover, zeolites loaded with lower Ag+ concentrations remain active down to 0.1 wt.%, and their activities are directly proportional to the total Ag content. Sequential exchanges with two metal ions (Ag+ and either Cu2+, Zn2+) display synergetic or antagonist effects, depending on the quantity of the second metal. Altogether, this work shows that, by combining analytical and quantitative methods, it is possible to fine-tune the composition of bi-metal-exchanged zeolites, in order to maximise their antimicrobial potential, opening new ways for the development of next-generation composite zeolite-containing antimicrobial materials, with potential applications for the design of dental or bone implants, as well as biomedical devices and pharmaceutical products.

Thermal CO Oxidation and Photocatalytic CO2 Reduction over Bare and M-Al2O3 (M = Co, Ni, Cu, Rh, Pd, Ag, Ir, Pt, and Au) Cotton-Like Nanosheets.

Aluminum oxide (Al2O3) has abundantly been used as a catalyst, and its catalytic activity has been tailored by loading transition metals. Herein, γ-Al2O3 nanosheets were prepared by the solvothermal method, and transition metals (M = Co, Ni, Cu, Rh, Pd, Ag, Ir, Pt, and Au) were loaded onto the nanosheets. Big data sets of thermal CO oxidation and photocatalytic CO2 reduction activities were fully examined for the transition metal-loaded Al2O3 nanosheets. Their physicochemical properties were examined by scanning electron microscopy, high-resolution transmission electron microscopy, X-ray diffraction crystallography, and X-ray photoelectron spectroscopy. It was found that Rh, Pd, Ir, and Pt-loading showed a great enhancement in CO oxidation activity while other metals negated the activity of bare Al2O3 nanosheets. Rh-Al2O3 showed the lowest CO oxidation onset temperature of 172 °C, 201 °C lower than that of bare γ-Al2O3. CO2 reduction experiments were also performed to show that CO, CH3OH, and CH4 were common products. Ag-Al2O3 nanosheets showed the highest performances with yields of 237.3 ppm for CO, 36.3 ppm for CH3OH, and 30.9 ppm for CH4, 2.2×, 1.2×, and 1.6× enhancements, respectively, compared with those for bare Al2O3. Hydrogen production was found to be maximized to 20.7 ppm during CO2 reduction for Rh-loaded Al2O3. The present unique pre-screening test results provided very useful information for the selection of transition metals on Al2O3-based energy and environmental catalysts.

A chemical and ecological assessment into elemental loading from ford crossings in Ashdown Forest, Sussex, United Kingdom.

Numerous studies have identified the issue of road surface runoff as a source of contamination into waterways but the impact of vehicular wash-off is less well understood. A ford crossing provides a pathway for vehicle-derived contaminants emanating from both road surface runoff and vehicular wash-off into a river system. Twyford Lane Ford (Ford 1) and Birchgrove Lane Ford (Ford 2), located ca. 600 m apart on a tributary of the River Ouse in Sussex (UK), were the focus of this study. A combination of biomonitoring (assessment of benthic macroinvertebrates) and chemical assessments of water and sediments has been undertaken to determine any detrimental impacts, such as a lack in biodiversity, resulting from the ford crossings. Sediment concentrations of chromium (Cr3+), lead (Pb) and zinc (Zn) were generally elevated at Ford 1, attenuating at sampling points between the fords to then peak at Ford 2. However, sediment particle size was seen to have an influence on elemental concentrations. In general, an increase in elemental concentrations was associated with a higher percentage of fine-grained sediments (≤63 µm). Elevated concentrations of Zn and magnesium (Mg) were identified within water samples taken during a precipitation event following a prolonged dry period. The biomonitoring results found reduced BMWP (Biological Monitoring Working Party) scores at positions close to the ford crossings, and where the stream was in proximity to the roadside. Sensitive Ephemeroptera were largely absent at sampling points closest to the fords, which is likely to be associated with elevated Zn. The results suggest that careful consideration should be applied when selecting crossing points over sensitive waters.

Noble metal nanoparticle-functionalized Zr-metal organic frameworks with excellent photocatalytic performance.

Noble metal nanoparticles (NPs) functionalized MOFs are attractive materials for photocatalytic reactions, and outstanding catalytic performances can be expected, especially when they have intrinsically matched crystal faces between metals and MOFs. This study discovered that the photocatalytic oxidation of aromatic alcohols to aldehydes was enhanced over Au/UiO-66-NH2 or Au/UiO-66 but suppressed over Pt loaded counterparts, whereas the reduction of Cr(VI) was boosted over both two catalysts. In reactions, the conversion of benzyl alcohol was 17.1% over UiO-66-NH2 and 7.6% over UiO-66, and an enhanced conversion was obtained over Au/UiO-66-NH2 (30.5%) and Au/UiO-66 (24.1%). However, the conversion was decreased over Pt/UiO-66-NH2 (9.3%) and Pt/UiO-66 (<1%). Experimental results revealed strong correlations between Zr-MOFs and loaded metal NPs, as Zr centers promoted the formation of Pt(200) planes that suppressed the production of ·O2- intermediates to oxidize aromatic alcohols, whereas Pt(200) exhibited no effect on the Cr(VI) reduction triggered by photo-induced electrons. The findings in this study on constructing noble metal NPs functionalized Zr-MOFs catalysts with specially-matched crystal structures and on distinguishing photocatalytic mechanisms on oxidation of alcohols and reduction of Cr(VI) would provide valuable information for designer (photo)catalysts based on MOFs and their applications in such as catalysis and environmental remediation.

Phytoremediation: Metal decontamination of soils after the sequential forestation of former opencast coal land.

Phytoremediation through forestry may be an effective means for reducing the metal loading in lands reclaimed after surface-coal-mining in the UK. Planted with mixed woodland, the soil loading of 5 key metals (Zn, Cd, Mn, Pb and Cu) decreased, significantly and progressively, compared to soils left as grassland through a 14 year forestation chronosequence on land reclaimed from the former Varteg opencast coalmine, South Wales. Fourteen years after initial tree planting, soil metal loadings decreased by 52% for Cd (4.3 mg∙kg-1 per year), 48% for Cu (2.1 mg∙kg-1 per year), 47% for Zn (7.3 mg∙kg-1 per year), 44% for Pb. (7.1 mg∙kg-1 per year) and 35% for Mn (45 mg.kg-1 per year). Analysis of metal loadings in the leaves of Alnus glutinosa (L. Gaertn) (Common Alder) and Betula pendula (Roth) (Silver Birch) found both to be involved in metal uptake with birch taking up more Cd, Cu, Zn and Mn and Alder more Pb. Concentrations of Zn, Mn and Cd (Birch only) increased significantly in leaves from, but not in soils, under older plantings. Since different tree species take up metals at different rates, mixed plantings may be more effective in forest phytoremediation.

Fabrication of Single-Atom Catalysts with Precise Structure and High Metal Loading.

In recent years, single-atom catalysts (SACs) have attracted particular interest and have been demonstrated to be a promising material in energy conversion and chemical transformation due to their optimal atom utilization and unique size quantum effect. The development of a versatile and simple synthetic approach for SACs is important for further investigation of their properties. In this regard, several physical and chemical methods have been developed to access SACs by varying the interaction between metal centers and the coordination defects of the supports. The common challenges for SACs in industrial applications are accurate control over the local structure of single sites and increasing the active-site density. On one hand, the rational design of the atomic structure is decisive to their intrinsic activity, which will affect the adsorption and activation of reactants over the single sites. On the other hand, increasing the metal loading of SACs would largely enhance the density of active sites and the corresponding mass activity, especially for industrial applications. Here, approaches to the synthesis of SACs-focusing on these two challenges-are highlighted.

Metal bioaccumulation and biomarkers of effects in caged mussels exposed in the Athabasca oil sands area.

The Athabasca oil sands deposit is the world's largest known reservoir of crude bitumen and the third-largest proven crude oil reserve. Mining activity is known to release contaminants, including metals, and to potentially impact the aquatic environment. The purpose of this study was to determine the impacts of oil sands mining on water quality and metal bioaccumulation in mussels from the Fort McMurray area in northern Alberta, Canada. The study presents two consecutive years of contrasting mussel exposure conditions (low and high flows). Native freshwater mussels (Pyganodon grandis) were placed in cages and exposed in situ in the Athabasca River for four weeks. Metals and inorganic elements were then analyzed in water and in mussel gills and digestive glands to evaluate bioaccumulation, estimate the bioconcentration factor (BCF), and determine the effects of exposure by measuring stress biomarkers. This study shows a potential environmental risk to aquatic life from metal exposure associated with oil sands development along with the release of wastewater from a municipal treatment plant nearby. Increased bioaccumulation of Be, V, Ni and Pb was observed in mussel digestive glands in the Steepbank River, which flows directly through the oil sands mining area. Increased bioaccumulation of Al, V, Cr, Co, Ni, Mo and Ni was also observed in mussel gills from the Steepbank River. These metals are naturally present in oil sands and generally concentrate and increase with the extraction process. The results also showed different pathways of exposure (particulate or dissolved forms) for V and Ni resulting from different river water flows, distribution coefficient (Kd) and BCF. Increasing metal exposure downstream of the oil sands mining area had an impact on metallothionein and lipid peroxidation in mussels, posing a potential environmental risk to aquatic life. These results confirm the bioavailability of some metals in mussel tissues associated with detoxification of metals (metallothionein levels), and oxidative stress in mussels located downstream of the oil sands mining area. These results highlight a potential ecotoxicological risk to biota and to the aquatic environment downstream of the oil sands mining area, even at low metal exposure levels.

Loading across the Periodic Table: Introducing 14 Different Metal Ions To Enhance Metal-Organic Framework Performance.

Loading metal guests within metal-organic frameworks (MOFs) via secondary functional groups is a promising route for introducing or enhancing MOF performance in various applications. In this work, 14 metal ions (Li+, Na+, K+, Mg2+, Ca2+, Ba2+, Zn2+, Co2+, Mn2+, Ag+, Cd2+, La3+, In3+, and Pb2+) have been successfully introduced within the MIL-121 MOF using a cost-efficient route involving free carboxylic groups on the linker. The local and long-range structure of the metal-loaded MOFs is characterized using multinuclear solid-state NMR and X-ray diffraction methods. Li/Mg/Ca-loaded MIL-121 and Ag nanoparticle-loaded MIL-121 exhibit enhanced H2 and CO2 adsorption; Ag nanoparticle-loaded MIL-121 also demonstrates remarkable catalytic activity in the reduction of 4-nitrophenol.

Enhanced photo-degradation of paracetamol on n-platinum-loaded TiO2: The effect of ultrasound and OH/hole scavengers.

Elimination/mineralization of paracetamol (PCT) was investigated by catalytic oxidation under ultrasound, UV and both. The catalyst was synthesized by immobilization of nPt on TiO2 to benefit from the ability of Pt to facilitate charge transfer processes and to separate e(-)/h(+) pairs. It was found that increasing the Pt-loading enhanced the rate of sonochemical reactions, but retarded that of photolytic reactions, due to reduced UV absorption on the surface. Simultaneous application of sonolysis and photolysis was synergistic due to disaggregation of the particles and homogenization of the active species over the catalyst surface. The decay of PCT was highly dependent on the availability of OH, as the reactions were nearly terminated in the presence of a strong OH scavenger-2-propanol. However, a remarkable rate enhancement was observed in the presence of a suitable dose of I(-), which scavenges both OH and hvb(+). The result was explained by the production of excess radicals upon sonolysis of iodide solutions, and the reactivity of PCT with them. Finally, carbon mineralization was significantly hindered in the presence of both scavengers due to increased competition for OH and inefficient formation of hydroquinone arising from reduced availability of hvb(+).

A method for apportionment of natural and anthropogenic contributions to heavy metal loadings in the surface soils across large-scale regions.

Quantification of the contributions from anthropogenic sources to soil heavy metal loadings on regional scales is challenging because of the heterogeneity of soil parent materials and high variability of anthropogenic inputs, especially for the species that are primarily of lithogenic origin. To this end, we developed a novel method for apportioning the contributions of natural and anthropogenic sources by combining sequential extraction and stochastic modeling, and applied it to investigate the heavy metal pollution in the surface soils of the Pearl River Delta (PRD) in southern China. On the average, 45-86% of Zn, Cu, Pb, and Cd were present in the acid soluble, reducible, and oxidizable fractions of the surface soils, while only 12-24% of Ni, Cr, and As were partitioned in these fractions. The anthropogenic contributions to the heavy metals in the non-residual fractions, even the ones dominated by natural sources, could be identified and quantified by conditional inference trees. Combination of sequential extraction, Kriging interpolation, and stochastic modeling reveals that approximately 10, 39, 6.2, 28, 7.1, 15, and 46% of the As, Cd, Cr, Cu, Ni, Pb, and Zn, respectively, in the surface soils of the PRD were contributed by anthropogenic sources. These results were in general agreements with those obtained through subtraction of regional soil metal background from total loadings, and the soil metal inputs through atmospheric deposition as well. In the non-residual fractions of the surface soils, the anthropogenic contributions to As, Cd, Cr, Cu, Ni, Pb, and Zn, were 48, 42, 50, 51, 49, 24, and 70%, respectively.