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Understanding the arsenic (As) enrichment mechanisms in the subsurface environment relies on a systematic investigation of As valence species and their partitioning with the Fe (oxyhydr)oxide phases in the subsoil profile. The present study explored the distribution, speciation, partitioning, and (im)mobilization of As associated with Fe in four subsoil cores (∼30 m depth) from Hong Kong using sequential chemical extraction and X-ray absorption near edge spectroscopy. The subsoil profiles exhibited relatively high concentrations of As at 26.1-982 mg/kg (median of 112 mg/kg), and the As was dominated by As(V) (85-96%) and primarily associated with the residual fraction (50.7-94.7%). A small amount of As (0.002-13.2 mg/kg) was easily mobilized from the four subsoil profiles, and a concentration of water-soluble As higher than 100 μg/L was observed for only some subsoil layers. The molar ratios of As:Fe in the oxalate-extractable Fe fraction ranged from 1.2 to 76.5 mmol/mol (median of 11.1 mmol/mol), revealing the participation of poorly crystalline Fe (oxyhydr)oxides in immobilizing most of the high geogenic As. The primary phases of ferric (oxyhydr)oxides were characterized as ferrihydrite (16-53%), lepidocrocite (0-32%), and goethite (0-62%), and these phases contributed to the sufficient ability of the subsoil to sequester 45.3-100% (median of 98.8%) of the exogenous As(V) (1.0 mg/L) in adsorption experiments. In contrast to As(V), exogenous As(III) showed a lower removal percentage (3.9-79.1%, median of 45.1%). The study revealed that the chemical speciation of As and Fe in the subsoil profiles is useful for predicting the immobilization of high geogenic As in the region, which is also helpful for the safe utilization of As-containing soil during land development worldwide.

Alkylated PAHs (APAHs) have been shown to be more toxic and persistent than their non-alkylated parent compounds. However, little is known about the extent of soil contamination by these pollutants. To help understand agricultural soil pollution by these compounds at a regional scale, a total of 18 methylated PAHs (MPAHs, a major class of APAHs) in 243 soil samples were analyzed. These soil samples were collected from 11 sites in the Yangtze River Delta (YRD) region, a representative fast developing area in China. The total concentration of MPAHs (∑18MPAHs) ranged from 5.5 to 696.2 ng/g dry soil, with methylnaphthalenes (M-NAPs) and methylphenanthrenes (M-PHEs) accounting for more than 70% of the compositional profile. Relatively high concentrations of ∑18MPAHs were found in Jiaxing and Huzhou areas of Zhejiang province, as well as on the border between the cities of Wuxi and Suzhou. Different MPAH groups showed dissimilar spatial distribution patterns. The spatial distribution of lower molecular weight MPAHs was related to agricultural straw burning and emissions/depositions from industrial activities, whereas that of higher molecular weight MPAHs was much more a function of the total organic carbon (TOC) content of soil. Although coal, biomass (crop straw and wood), and petroleum combustion were identified to be the major emission sources for most of the sampling sites, the areas with relatively severe pollution with ∑18MPAHs resulted from the localized hotspots of petroleum leakage. Isomeric MPAHs with methyl group substituted at 2- (β) position exhibited significantly higher concentrations than those substituted at 1- (α) position. Results of this work help to understand soil pollution by MPAHs, and are useful for designing effective strategies for pollution control so as to ensure food safety in areas with fast economic growth.

Fine particle (PM 2.5 ) samples were collected simultaneously at three urban sites (Shanghai, Nanjing, and Hangzhou) and one rural site near Ningbo in the Yangtze River Delta (YRD) region, China, on a weekly basis from September 2013 to August 2014. In addition, high-frequency daily sampling was conducted in Shanghai and Nanjing for one month during each season. Severe regional PM 2.5 pollution episodes were frequently observed in the YRD, with annual mean concentrations of 94.6 ± 55.9, 97.8 ± 40.5, 134 ± 54.3, and 94.0 ± 57.6 μg m −3 in Shanghai, Nanjing, Hangzhou, and Ningbo, respectively. The concentrations of PM 2.5 and ambient trace metals at the four sites showed clear seasonal trends, with higher concentrations in winter and lower concentrations in summer. In Shanghai, similar seasonal patterns were found for organic carbon (OC), elemental carbon (EC), and water-soluble inorganic ions (K + , NH 4 + , Cl − , NO 3 − , and SO 4 2- ). Air mass backward trajectory and potential source contribution function (PSCF) analyses implied that areas of central and northern China contributed significantly to the concentration and chemical compositions of PM 2.5 in Shanghai during winter. Three heavy pollution events in Shanghai were observed during autumn and winter. The modelling results of the Nested Air Quality Prediction Modeling System (NAQPMS) showed the sources and transport of PM 2.5 in the YRD during the three pollution processes. The contribution of secondary species (SOC, NH 4 + , NO 3 − , and SO 4 2- ) in pollution event (PE) periods was much higher than in BPE (before pollution event) and APE (after pollution event) periods, suggesting the importance of secondary aerosol formation during the three pollution events. Furthermore, the bioavailability of Cu, and Zn in the wintertime PM 2.5 samples from Shanghai was much higher during the pollution days than during the non-pollution days.

Although benzovindiflupyr (BZF), which is a novel succinate dehydrogenase inhibitor fungicide, has considerable application potential worldwide, its extensive use is toxic to non-targeted soil organisms. Therefore, this study aimed to evaluate the acute and subchronic toxicity of BZF to earthworms (Eisenia fetida). The acute toxicity of BZF to adult and larval earthworms was measured, as indicated by the following LC50 values obtained after 14 days of exposure: 416 mg/kg for adult earthworms and 341 mg/kg for juveniles. Subchronic toxicity tests were conducted using only adult earthworms. The earthworms’ weight gain was slower on days 14 and 28 after commencing the BZF T100 treatment (50 mg/kg of soil). Following 14 days of BZF exposure, enzymes and gene expressions associated with the mitochondrial respiratory chain and energy metabolism were activated to some extent, and the reactive oxygen species level and malondialdehyde content also increased. Antioxidant and detoxifying enzymes and metallothionein gene, Heat shock protein 70 gene associated with resistance to oxidative damage were also activated to varying degrees. Increased BZF concentrations corresponded to increased genotoxicity. Integrated biological response (IBR) values were calculated at the biochemical and molecular levels to show increased toxicity with increased BZF concentration. Although a series of biomarkers changes occurred after initiating BZF treatment, these changes were all likely to have been resisted by the earthworms’ own antioxidant defense system and only showed phenotypic (weight-related) changes with treatments of 50 mg/kg. In conclusion, reasonable levels of BZF application may have little impact on earthworms. Our findings provide insights on the toxic effects of BZF on earthworms and may prove useful for risk assessments relating to BZF’s impacts on soil ecosystems.

The biodegradable S,S-ethylenediaminedisuccinic acid (EDDS) is a promising chelant for chelant-assisted phytoextraction of trace metals in polluted soil. The interactions between EDDS and trace metals/major elements in the soil affect the metal bioavailability and their subsequent phytoextraction efficiency. This study aimed to investigate the macroscopic and molecular-level interactions of EDDS with Cu in the rhizosphere and non-rhizosphere of a Cu-polluted agricultural soil. A multi-interlayer rhizobox planted with ryegrass was used to simulate the transport of EDDS and Cu from the non-rhizosphere to rhizosphere soils. The results showed that EDDS (5 mM kg−1) significantly dissociated Cu (285–690 fold), Fe (by 3.47–60.2 fold), and Al (2.43–5.31 fold) from the soil in comparison with a control group. A combination of micro-X-ray fluorescence, X-ray absorption near-edge structure spectroscopy, and sequential extraction analysis revealed that EDDS primarily chelated the adsorbed fraction of Cu by facilitating the dissolution of goethite. Moreover, as facilitated by ryegrass transpiration, CuEDDS was moved from the non-rhizosphere to rhizosphere and accumulated in ryegrass. In situ processes of Cu extraction and transport by EDDS in the rhizosphere were further elucidated with chemical speciation analysis and geochemical modeling methods.

In health-oriented air pollution control, it is vital to rank the contributions of different emission sources to the health risks posed by hazardous components in airborne fine particulate matters (PM2.5), such as trace metals. Towards this end, we investigated the PM2.5-associated metals in two densely populated regions of China, the Yangtze River Delta (YRD) and Pearl River Delta (PRD) regions, across land-use gradients. Using the positive matrix factorization (PMF) model, we performed an integrated source apportionment to quantify the contributions of the major source categories underlying metal-induced health risks with information on the bioaccessibility (using simulated lung fluid) and speciation (using synchrotron-based techniques) of metals. The results showed that the particulate trace metal profiles reflected the land-use gradient within each region, with the highest concentrations of anthropogenically enriched metals at the industrial sites in the study regions. The resulting carcinogenic risk that these elements posed was higher in the YRD than in the PRD. Chromium was the dominant contributor to the total excessive cancer risks posed by metals while manganese accounted for a large proportion of non-carcinogenic risks. An elevated contribution from industrial emissions was found in the YRD, while traffic emissions and non-traffic combustion (the burning of coal/waste/biomass) were the common dominant sources of cancer and non-cancer risks posed by metals in both regions. Moreover, the risk-oriented source apportionment of metals did not mirror the mass concentration-based one, suggesting the insufficiency of the latter to inform emission mitigation in favor of public health. While providing region-specific insights into the quantitative contribution of major source categories to the health risks of PM2.5-associated trace metals, our study highlighted the need to consider the health protection goal-based source apportionment and emission mitigation in supplement to the current mass concentration-based framework.

Ten antibiotics belonging to three groups (macrolides, fluoroquinolones and sulfonamides) were investigated in riverine runoff of the Pearl River Delta (PRD) and Pearl River Estuary (PRE), South China for assessing the importance of riverine runoff in the transportation of contaminants from terrestrial sources to the open ocean. All antibiotics were detected in the eight outlets with concentrations ranging from 0.7 to 127 ng L-1. The annual mass loadings of antibiotics from the PRD to the PRE and coast were 193 tons with 102 tons from the fluoroquinolone group. It showed that antibiotics decreased from the riverine outlets to the PRE and open ocean. Risk assessment showed that most of these antibiotics showed various ecological risks to the relevant aquatic organisms, in which ofloxacin (OFL), erythromycin (ETM) and ciprofloxacin (CIP) posed high ecological risks to the studied aquatic environments. (C) 2013 Elsevier Ltd. All rights reserved.

In this study, a novel in situ sampling method was utilized to investigate the concentrations of trace metals and Pb isotope compositions among different particle size fractions in soil dust, bulk surface soil, and corresponding road dust samples collected within an urban environment. The aim of the current study was to evaluate the feasibility of using soil dust samples to determine trace metal contamination and potential risks in urban areas in comparison with related bulk surface soil and road dust. The results of total metal loadings and Pb isotope ratios revealed that soil dust is more sensitive than bulk surface soil to anthropogenic contamination in urban areas. The new in situ method is effective at collecting different particle size fractions of soil dust from the surface of urban soils, and that soil dust is a critical indicator of anthropogenic contamination and potential human exposure in urban settings.

One concern about the chelant-enhanced phytoextraction is the potential metal leaching associated with chelant application. A field study was carried out and the metal leaching along the 60-cm depth soil profiles were evaluated within 36 days after the biodegradable chelant EDDS was applied. Results showed EDDS significantly increased soluble Cu in the top 5 cm soil layer 1 day after the application, and the increase of soluble metals was generally limited in the top 20 cm soil. Metal speciation analysis indicated all Cu and Zn were in forms of Cu-EDDS and Zn-EDDS complexes in soil solution, and Ca was the major competitor with trace metals to EDDS. The soluble metals decreased quickly with time, and no significant difference was observed in the extractable Cu between EDDS treatments and the controls 22 days after the EDDS addition. The potential leaching associated with biodegradable EDDS addition may be controlled under field conditions.

The concentration and composition of PBDEs in the soils and plants near a typical e-waste recycling site in South China were investigated. The total concentration of PBDEs (ΣPBDEs) in soil ranged from 4.8 to 533 ng/g dry wt. The ΣPBDEs in vegetation were from 2.1 to 217 ng/g dry wt. For the vegetable, the highest concentration of 19.9 ng/g dry wt. was observed in the shoot of Brassica alboglabra L. BDE 209 was the predominant congener in all samples. In comaprison with other e-waste contaminated sites in China, lower concentrations of PBDEs and higher concentrations of PCBs were observed in both soils and plants suggesting different e-waste types involved in the present study. The PBDEs contaminated vegetables around the e-waste dismantling site may pose a potential health risk to the local inhabitants.

The spatial and temporal variations of mercury (Hg) in sediments of the Pearl River Estuary (PRE) and the surrounding coastal area (South China Sea) were studied. In surface sediments, the concentrations of Hg ranged from 1.5 to 201 ng/g, with an average of 54.4 ng/g, displaying a decreasing trend with the distance from the estuary to the open sea. This pattern indicates that the anthropogenic emissions from the Pearl River Delta (PRD) region are probably the main sources of Hg in this coastal region. Using the (210)Pb dating technique, the historical changes in the concentrations and influxes of Hg in the last 100 years were also investigated. The variations in Hg influxes in sediment cores obviously correlate with the economic development and urbanization that has occurred the PRD region, especially in the last three decades. (C) 2010 Elsevier Ltd. All rights reserved.

Plants grown in contaminated areas may accumulate trace metals to a toxic level via their roots and/or leaves. In the present study, we investigated the distribution and sources of Pb and Cd in maize plants (Zea mays L.) grown in a typical zinc smelting impacted area of southwestern China. Results showed that the smelting activities caused significantly elevated concentrations of Pb and Cd in the surrounding soils and maize plants. Pb isotope data revealed that the foliar uptake of atmospheric Pb was the dominant pathway for Pb to the leaf and grain tissues of maize, while Pb in the stalk and root tissues was mainly derived from root uptake. The ratio of Pb to Cd concentrations in the plants indicated that Cd had a different behavior from Pb, with most Cd in the maize plants coming from the soil via root uptake.

Urban lakes are vulnerable to the accumulation of semivolatile organic compounds, such as PAHs from wet and dry atmospheric deposition. Little was reported on the seasonal patterns of atmospheric deposition of PAHs under Asian monsoon climate. Bulk (dry + wet) particle deposition, air–water diffusion exchange, and vapour wet deposition of PAHs in a small urban lake in Guangzhou were estimated based on a year-round monitoring. The total PAH particle deposition fluxes observed were 0.44–3.46 μg m −2 day −1 . The mean air–water diffusive exchange flux was 20.7 μg m −2 day −1 . The vapour deposition fluxes of PAHs ranged 0.15–8.26 μg m −2 day −1 . Remarkable seasonal variations of particulate PAH deposition, air–water exchange fluxes and vapour wet deposition were influenced by seasonal changes in meteorological parameters. The deposition fluxes were predominantly controlled by the precipitation intensity in wet season whereas by atmospheric concentration in dry season.

Nine selected antibiotics in the Victoria Harbour of Hong Kong and the Pearl River at Guangzhou, South China, were analyzed using high-performance liquid chromatography-electrospray ionization tandem mass spectrometry. The results showed that the concentrations of antibiotics were mainly below the limit of quantification (LOQ) in the marine water of Victoria Harbour. However, except for amoxicillin, all of the antibiotics were detected in the Pearl River during high and low water seasons with the median concentrations ranging from 11 to 67 ng/L, and from 66 to 460 ng/L, respectively; and the concentrations in early spring were about 2-15 times higher than that in summer with clearer diurnal variations. It was suggested that the concentrations of antibiotics in the high water season were more affected by wastewater production cycles due to quick refreshing rate, while those in the low water season may be more sensitive to the water column dynamics controlled by tidal processes in the river.

The potential of 18 different plants to be used in the chemically enhanced phytoextraction of Cu, Pb, Zn and Cd was assessed using pot experiments. Chrysanthemum coronarium L. was the species most sensitive to the application of EDTA, and had the highest enhancement of Cu and Pb concentrations in its shoots. Compared with EDTA, EDDS was more effective in enhancing the concentration of Cu in the shoots of Chrysanthemum coronarium L. and Zea mays L. grown on multi-metal contaminated soils. The EDTA-treated soil still had a significant ability to enhance the concentrations of Cu and Pb in the shoots of Zea mays L. six months after the chelant treatment. However, the EDDS-treated soil did not have any effect in enhancing the concentrations of metals in the shoots of Zea mays L. in the second crop test. The results may indicate that EDDS biodegrades more rapidly than EDTA in soil and is better in limiting potential metal leaching.

As the world's urban population continues to grow, it becomes increasingly imperative to understand the dynamic interactions between human activities and the urban environment. The development of urban environmental geochemistry has yielded a significant volume of scientific information about geochemical phenomena found uniquely in the urban environment, such as the distribution, dispersion, and geochemical characteristics of some toxic and potentially toxic trace metals. The aim of this paper is to provide an overview of the development of urban environmental geochemistry as a field of scientific study and highlight major transitions during the course of its development from its establishment to the major scientific interests in the field today. An extensive literature review is also conducted of trace metal contamination of the urban terrestrial environment, in particular of urban soils, in which the uniqueness of the urban environment and its influences on trace metal contamination are elaborated. Potential areas of future development in urban environmental geochemistry are identified and discussed.

The rapid economic development in the Pearl River Delta (PRD) region in South China in the last three decades has had a significant impact on the local environment. Estuarine sediment is a major sink for contaminants and nutrients in the surrounding ecosystem. The accumulation of trace metals in sediments may cause serious environmental problems in the aquatic system. Thirty sediment cores were collected in the Pearl River Estuary (PRE) in 2000 for a study on trace metal pollution in this region. Heavy metal concentrations and Pb isotopic compositions in the four 210Pb-dated sediment cores were determined to assess the fluxes in metal deposits over the last one hundred years. The concentrations of Cu, Pb and Zn in the surface sediment layers were generally elevated when compared with the sub-surface layers. There has been a significant increase in inputs of Cu, Pb and Zn in the PRE since the 1970s. The results also showed that different sampling locations in the estuary received slightly different types of inputs. Pb isotopic composition data indicated that the increased Pb in the recent sediments was of anthropogenic origin. The results of trace metal influxes showed that about 30% of total Pb and 15% of total Zn in the sediments in the 1990s were from anthropogenic sources. The combination of trace metal analysis, Pb isotopic composition and 210Pb dating in an estuary can provide vital information on the long-term accumulation of metals in sediments.

There is a growing public concern over the potential accumulation of heavy metals in agricultural soils in China owing to rapid urban and industrial development and increasing reliance on agrochemicals in the last several decades. Excessive accumulation of heavy metals in agricultural soils may not only result in environmental contamination, but elevated heavy metal uptake by crops may also affect food quality and safety. The present study is aimed at studying heavy metal concentrations of crop, paddy and natural soils in the Pearl River Delta, one of the most developed regions in China. In addition, some selected soil samples were analyzed for chemical partitioning of Co, Cu, Pb and Zn. The Pb isotopic composition of the extracted solutions was also determined. The analytical results indicated that the crop, paddy and natural soils in many sampling sites were enriched with Cd and Pb. Furthermore, heavy metal enrichment was most significant in the crop soils, which might be attributed to the use of agrochemicals. Flooding of the paddy soils and subsequent dissolution of Mn oxides may cause the loss of Cd and Co through leaching and percolation, resulting in low Cd and Co concentrations of the paddy soils. The chemical partitioning patterns of Pb, Zn and Cu indicated that Pb was largely associated with the Fe-Mn oxide and residual fractions, while Zn was predominantly found in the residual phase. A significant percent fraction of Cu was bound in the organic/sulphide and residual phases. Based on the 206Pb/207Pb ratios of the five fractions, it was evident that some of the soils were enriched with anthropogenic Pb, such as industrial and automobile Pb. The strong associations between anthropogenic Pb and the Fe-Mn oxide and organic/sulphide phases suggested that anthropogenic Pb was relatively stable after deposition in soils.