Integrated assessment of land-to-river Cd fluxes and riverine Cd loads using SWAT-HM to guide management strategies.

In 2011, China invested US$9.8 billion to combat the severe heavy metal pollution in the Xiang River basin (XRB), aiming to reduce 50% of the 2008 industrial metal emissions by 2015. However, river pollution mitigation requires a holistic accounting of both point and diffuse sources, yet the detailed land-to-river metal fluxes in the XRB remain unclear. Here, by combining emissions inventories with the SWAT-HM model, we quantified the land-to-river cadmium (Cd) fluxes and riverine Cd loads across the XRB from 2000 to 2015. The model was validated against long-term historical observations of monthly streamflow and sediment load and Cd concentrations at 42, 11, and 10 gauges, respectively. The analysis of the simulation results showed that the soil erosion flux dominated the Cd exports (23.56-80.14 Mg yr-1). The industrial point flux decreased by 85.5% from 20.84 Mg in 2000 to 3.02 Mg in 2015. Of all the Cd inputs, approximately 54.9% (37.40 Mg yr-1) was finally drained into Dongting Lake; the remaining 45.1% (30.79 Mg yr-1) was deposited within the XRB, increasing the Cd concentration in riverbed sediment. Furthermore, in XRB's 5-order river network, the Cd concentrations in small streams (1st order and 2nd order) showed larger variability due to their low dilution capacity and intense Cd inputs. Our findings highlight the need for multi-path transport modeling to guide future management strategies and better monitoring schemes to restore the small polluted streams.

Identification priority source of soil heavy metals pollution based on source-specific ecological and human health risk analysis in a typical smelting and mining region of South China.

An in-depth understanding of the ecological and health risks posed by heavy metals originating from various pollution sources is critical for foresighted soil-quality management. Based on 220 grid samples (2 × 2 km) analyzed for eight heavy metals (Cd, Hg, As, Pb, Cr, Ni, Cu, and Zn) in the Chenshui (CS) watershed of Hunan Province, China, we applied an integrated approach for identifying and apportioning pollution sources of soil heavy metals and exploring their source-specific pollution risks. This approach consists of three sequential steps: (1) source identification by combining the positive matrix factorization model with geostatistical analysis; (2) quantification of ecological, carcinogenic, and non-carcinogenic risks in a source-specific manner; (3) prioritization of sources in a holistic manner, considering both ecological risks and human health risks. Cd (68.0%) and Hg (13.3%) dominated the ecological risk in terms of ecological risk index; As dominated the non-carcinogenic health risk in terms of total hazard index (THI; adults: 84.8%, children: 84.7%) and the carcinogenic health risk in terms of total carcinogenic risk index (TCRI; adults: 69.0%, children: 68.8%). Among three exposure routes, oral ingestion (89.4-95.2%) was the predominant route for both adults and children. Compared with adults (THI = 0.41, TCRI = 7.01E-05), children (THI = 2.81, TCRI = 1.22E-04) had greater non-carcinogenic and carcinogenic risks. Four sources (F1-4) were identified for the CS watershed: atmospheric deposition related to coal-burning and traffic emissions (F1, 18.0%), natural sources from parent materials (F2, 34.3%), non-ferrous mining and smelting industry (F3, 37.9%), and historical arsenic-related activity (F4, 9.8%). The F3 source contributed the largest (45.2%) to the ecological risks, and the F4 source was the predominant contributor to non-carcinogenic (52.4%) and carcinogenic (64.6%) risks. The results highlight the importance of considering legacy As pollution from abandoned industries when developing risk reduction strategies in this region. The proposed methodology for source and risk identification and apportionment formulates the multidimensional concerns of pollution and the various associated risks into a tangible decision-making process to support soil pollution control.

The characteristics of oestrone mobility in water and soil by the addition of Ca-biochar and Fe-Mn-biochar derived from Litchi chinensis Sonn.

In this study, the effect of biochar (BC) derived from Litchi chinensis Sonn. and its modification, including Ca-biochar (Ca-BC) and Fe-Mn-biochar (Fe-Mn-BC), on the transportation of oestrone (E1) in water and soil was investigated. Fe-Mn-BC showed better adsorption ability than other types of biochar (BC, Ca-BC) under different conditions (humic acid, pH, ionic strength) in an aqueous environment. The maximum mass of sorbent at 298 K increased from 1.12 mg g-1 (BC) to 4.18 mg g-1 (Fe-Mn-BC). Humic acid had a greater impact on aqueous E1 adsorption on these biochars than did the pH and ionic strength. Fe-Mn-BC as a soil amendment had a great control of E1 transport in soil, and no leachate of E1 was observed in the column experiment. E1 mobility showed strong retardation in amended soil with Ca-BC (Rf = 11.2) compared with raw soil (Rf = 7.1). These results suggested that Fe-Mn-BC was more effective in controlling E1 transportation, and Fe-Mn-BC could be used as an alternative and inexpensive adsorbent to reduce E1 contaminants from water and soil.

Occupational exposure characteristics and health risk of PBDEs at different domestic e-waste recycling workshops in China.

Polybrominated diphenyl ethers (PBDEs) contained in electronic waste (e-waste) can be released to indoor environments and cause occupational health hazards during the recycling process. TVs, washing machines, refrigerators and printed wiring boar (PWB) represent the main domestic e-wastes. In this study, concentrations of Σ7PBDEs in air and dust samples from recycling workshops handling these four major types of e-wastes were measured, and the occupational exposure risk for workers at the corresponding workshops was evaluated. Concentrations of Σ7PBDEs in air and dust were within the ranges of 55.28-369.66 ng/m3 and 158.07-669.81 µg/g, respectively. The highest concentration of Σ7PBDEs in air was detected in the TV recycling workshop, while the refrigerator recycling workshop had the highest level of Σ7PBDEs in dust. The workers at these two e-waste recycling workshops were the most substantially exposed to BDE-209, which accounted for more than 85% of Σ7PBDEs in both air and dust. Compared to other e-waste recycling workshops, the workers at the PWB recycling workshop were also more exposed to BDE-47 and BDE-99. Occupational exposure levels for inhalation and dust ingestion were within the ranges of 3939 pg/kg/d to 26,271 pg/kg/d and 104,945 pg/kg/d to 444,694 pg/kg/d, respectively. The hazard quotient (HQ) values were calculated based on the RfDs provided by the EPA. Total HQ levels of inhalation exposure and dust ingestion were less than 0.222. The results of the HQ indicated that no adverse health effects were expected for workers in these workshops; however, the exposure risk of workers in the PWB recycling workshop (HQ=0.222) was higher than that in other e-waste recycling workshops (HQ=0.022-0.072). At the PWB recycling workshop, BDE-47 and BDE-99 caused the main occupational exposure risk to the workers, while s in the recycling plants handling other types of domestic e-waste BDE-209 was the major contributor to the risk faced by the workers.

Modeling transport and fate of heavy metals at the watershed scale: State-of-the-art and future directions.

A predictive understanding of the source-specific (e.g., point and diffuse sources) land-to-river heavy metal (HM) loads and HM dynamics in rivers is essential for mitigating river pollution and developing effective river basin management strategies. Developing such strategies requires adequate monitoring and comprehensive models based on a solid scientific understanding of the watershed system. However, a comprehensive review of existing studies on the watershed-scale HM fate and transport modeling is lacking. In this review, we synthesize the recent developments in the current generation of watershed-scale HM models, which cover a wide range of functionalities, capabilities, and spatial and temporal scales (resolutions). Existing models, constructed at various levels of complexity, have their strengths and weaknesses in supporting diverse intended uses. Additionally, current challenges in the application of watershed HM modeling are covered, including the representation of in-stream processes, organic matter/carbon dynamics and mitigation practices, the issues of model calibration and uncertainty analysis, and the balance between model complexity and available data. Finally, we outline future research requirements regarding modeling, strategic monitoring, and their combined use to enhance model capabilities. In particular, we envisage a flexible framework for future watershed-scale HM models with varying degrees of complexity to accommodate the available data and specific applications.

The toxicity of cadmium (Cd²âº) towards embryos and pro-larva of soldatov's catfish (Silurus soldatovi).

A six-day static-renewal toxicity test was performed to determine the influences of cadmium on the development of embryos of soldatov's catfish (Silurus soldatovi). The median lethal concentration (LC50) value and median effective concentration (EC50, i.e., the total adverse effects, including developmental defects and mortality) were calculated to be 2740 and 133 µg/L, respectively, when cadmium was prepared in dilution water. The LC50 decreased to 266 µg/L in a subsequent test one month later, thereby suggesting that the sensitivity of this fish to cadmium in the early life stage(1) was largely influenced by the quality of fertilized eggs, which is known to be dependent on the season. The mortality and total adverse effects showed a concentration-dependent relationship at dosages greater than 1000 or 10 µg/L (p<0.05), respectively, at pro-larva stage (i.e., 144 hpf) with dilution water. To compare the toxic effects of cadmium under field and experimental conditions, filtered river water was adopted as a solvent simultaneously compared with dilution water. No significant differences were observed in mortality rate, hatching rate and adverse effect prevalence between the two solvents. In comparison to previously published toxicity data for other fish, the pro-larva of soldatov's catfish were less sensitive than established test fish in the early life stage. Therefore, the environmental risks would be overestimated when considering only existing toxicity data for other test fish.

An all-in-one tool for multipurpose ecological risk assessment and management (MeRAM) of chemical substances in aquatic environment.

A quality-assured ecological risk assessment (ERA) requires enormous resources (time and labor) in collection/assessment of hazard data, as well as considerable expertise to interpret the risk. The ERA of chemicals is thereby considered difficult or impossible for those with little assessment experience and cumbersome or complicated for practitioners. To meet the concerns regarding ERA and accelerate the risk assessment and management of chemicals, we developed an all-in-one free tool for multi-purpose ecological risk assessment management (MeRAM) of chemical substances in aquatic environment called the AIST-MeRAM Ver. 2.0.0 (Copyright No: H28PRO-2007). It allows users from beginners to experts to conduct ERA without any preparation because all the necessary ecotoxicity test data and methodologies are available in the system. Approximately 270,000 ecotoxicity test data points for 3900 chemical substances together with the scientific methodologies from traditional simple hazard quotient (HQ) to more ecologically relevant complicated assessments such as species sensitivity distribution (SSD) and population-level assessment are embedded in the AIST-MeRAM. In addition, users can easily understand the Japanese regulatory RA and management of chemical substances due to a special function based on the Japanese Chemical Substance Control Law (CSCL). Here, we demonstrate a tiered ERA using the embedded sample data to evaluate and ensure the functions of AIST-MERAM. We show that the AIST-MeRAM can provide a comprehensive and accurate ERA, suggesting that it is a powerful IT solution for cumbersome ERA.

Surface water quality and its control in a river with intensive human impacts--a case study of the Xiangjiang River, China.

Surface water quality and its natural and anthropogenic controls in the Xiangjiang River were investigated using multivariate statistical approaches and a comprehensive observation dataset collected from 2004 to 2008. Cluster analysis (CA) grouped the 15 different sampling stations into five clusters with similar hydrochemistry characteristics and pollution levels. Four principal components (PCs), nutrients, heavy metals, natural components, and organic components, were extracted from the entire dataset. Comparison of the different regional characteristics of these four PCs revealed a decreasing trend for heavy metals and an increasing trend for organic factor on an annual scale, and the seasonal trend was only observed for natural factor. We also conducted analysis of variance (ANOVA) in combination with principal component analysis (PCA) to quantify the relative contribution of spatial and temporal variations to each of the four PCs. The results revealed that 62% of the contributions from the spatial sites were responsible for variations in heavy metals, while 83% of the contributions from the sampling time were responsible for natural variations observed. However, no significant spatial or temporal contributions were found to be responsible for the nutrient and organic variations. Finally, some suggestions regarding water management were put forward based on the current status and future trends of surface water quality in the Xiangjiang River.

Extrapolation of available acute and chronic toxicity test data to population-level effects for ecological risk management of chemicals.

An extrapolation approach is proposed using available acute (median lethal or effect concentration) and chronic (no-observed-effect concentration) toxicity test data at the organism level to derive a reference value contributing to the development of predicted-no-effect concentration on population persistence for population-level ecological risk assessment of chemicals. A matrix population model of wild medaka (Oryzias latipes) was employed as the tool to integrate the available organism-level toxicity test data on reproduction and survival into a finite population growth rate (lambda) that provides information regarding the status of the population persistence. After demonstrating the approach using the acute and chronic toxicity test data of alcohol ethyxolate on fish to calculate the reference value defined as the concentration at lambda = 1 (C(lambda=1)), the proposed approach was then evaluated by a comparison of the C(lambda=1) value derived by the extrapolation approach to those C(lambda=1) values calculated by two other approaches, in which different amounts of toxicity information contained in the same full life-cycle toxicity test data set on 4-nonylphenol were employed. It was concluded that this extrapolation approach is widely applicable and is promising for performing population-level ecological risk assessment on a more general basis that can support reasonable chemical management.

A feed-forward artificial neural network for prediction of the aquatic ecotoxicity of alcohol ethoxylate.

A feed-forward artificial neural network (ANN) has been developed for predicting the aquatic ecotoxicity of alcohol ethoxylate (AE), a non-ionic surfactant comprising a variety of homologues. Trained with previously reported ecotoxicity data, the ANN utilizes both molecular characteristics (alkyl chain length, branching extent in alkyl chain, and ethoxylate (EO) number) and exposure features (effect endpoint, test duration, test type, and species taxon) as inputs to predict the ecotoxicity. The ANN predicted an increase in ecotoxicity for homologues with a longer or less-branched alkyl chain, or those with fewer EO units. But for long alkyl chain (>14) homologues, the ecotoxicity increase was predicted by the ANN to level off, which is obscured by existing quantitative structure-activity relationships (QSARs). A "leave-one-out" cross-validation process indicated that the prediction accuracy was within a factor of 5 with 90% probability. This research demonstrated that the current ANN covers a wider application domain with respect to the homologue range and a variety of exposure features without compromising on predictive accuracy.

A heavy metal module coupled with the SWAT model and its preliminary application in a mine-impacted watershed in China.

Heavy metal behavior in soil and water requires modeling for a better understanding of the potential adverse impacts on the ecosystem as well as on humans. A heavy metal transport and transformation module is combined with the well-established SWAT (Soil and Water Assessment Tool) model for the purpose of simulating the fate and transport of metals at the watershed scale. The heavy metal module accounts for sorption, complexation and slow reactions among metal species; the heavy metals in the upland are allowed to transport vertically through percolation and evaporation-induced water rising as well as horizontally through soil erosion and surface/subsurface runoff; the heavy metals in the water body, in contrast, are modeled to undergo settling, resuspension, diffusion and burial processes. As a demonstration, the SWAT-laden heavy metal module (SWAT-HM) was calibrated to simulate zinc (Zn) and cadmium (Cd) dynamics in an upstream watershed of the Liuyang River in China, which has been impacted by mining activities for decades. The model simulations were found to agree reasonably well with the monitored results. In particular, the elevation of metal loads in channels with precipitation events was well represented, demonstrating that a considerable amount of Zn and Cd in the waste rock dumps and contaminated soil was released into rivers through rainfall. After a simulation of 6years (2009-2014), the simulated Zn and Cd concentrations were used as a surrogate for the Predicted Environmental Concentration (PEC), whereby an ecological risk assessment was conducted for the demonstrative mining area. This initiative toward developing a heavy metal module combined with SWAT has high potential for application in environmental risk analysis and pollution control.

Distributions and ecological risk assessment of estrogens and bisphenol A in an arid and semiarid area in northwest China.

Free estrogens (estrone, E1; 17ß-estradiol, 17ß-E2; estriol, E3; and 17α-ethinylestradiol, EE2), their corresponding sulfate and glucuronide conjugates, and bisphenol A (BPA) were investigated in water and sediments in the Fen River catchment, an arid and semiarid area in northwest China. E1 and BPA were frequently detected in the wet and dry sampling seasons. In addition to the sulfate conjugates, other conjugated estrogens were not detected in water and sediments. The concentrations of these compounds in water generally increased from upstream to downstream. The concentrations in water samples of most sites were higher in the wet season than those in the dry season, but concentrations in sediments of most sites were higher in the dry season than those in the wet season. The distributions of these compounds in sediments were positively correlated with the total organic carbon (TOC) contents of sediments (0.3 < R 2 < 0.6, p < 0.01) and concentrations in water (0.25 < R 2 < 0.50, p < 0.01). In this catchment, E1 was the main contributor to endocrine disrupting risk. The surface water in most of the tributaries and the sewage in the drainage channels were at risk. The pore waters of sediments were at risk at most sampling sites.

Kinetic study and modeling on photocatalytic degradation of para-chlorobenzoate at different light intensities.

In order to clarify the dependence of apparent adsorption constant Ks in the Langmuir-Hinshelwood (L-H) model on the incident light intensity, photocatalytic degradation kinetic characteristics were experimentally investigated at different light intensities using para-chlorobenzoate (4-CBA) as a model compound. In all cases 4-CBA initial degradation rates showed dependence on 4-CBA initial concentration, which can be described by the L-H model. However, the adsorption constant Ks and rate constant kr obviously varied with light intensity. To account for the experimental finding, slight modification of the classic kinetic model developed by Turchi and Ollis was tentatively proposed by assuming insufficiency of H2O/OH- available for photo-activated holes' scavenging. Such a kinetic model predicts that both k(r) and Ks(-1) are linearly proportional to the square root of the intensity in a rather large intensity range. The validity of the modified model was proved by fitting it to the experimental data.