基于重金属有效态的农田土壤重金属污染评价研究

目前农田土壤重金属污染评价以重金属全量为依据,而评价农田土壤重金属污染影响时主要考虑农产品安全从而保障人体健康,农作物对重金属的吸收积累量则取决于土壤中有效态重金属含量。在阐述土壤重金属有效态定义的基础上,综合分析了土壤重金属有效态的影响因素及其与土壤中重金属全量和农作物中重金属含量的相关性,概括了土壤重金属有效态在土壤重金属污染评价中的应用,以期提出建立以土壤重金属有效态含量为基础、结合土壤重金属全量及作物中吸收的重金属含量的土壤重金属污染评价体系。     

The identification of readily bioavailable pollutants in lake shkodra/skadar using semipermeable membrane devices (SPMDs), bioassays and chemical analysis

GOAL, SCOPE AND BACKGROUND: Lake Shkodra/Skadar is the largest lake in the Balkans region and located on the border between Albania to the south and Montenegro to the north. Because of the wide range of endemic, rare or endangered plant and animal species it supports, Lake Shkodra/Skadar and its extensive associated wetlands are internationally recognised as a site of significance and importance (Ramsar site). In recent years, social and economic changes in both Albania and Montenegro have lead to unprecedented levels of urban and industrial effluent entering the lake. Of particular concern is the increasing input of toxic hydrophobic organic pollutants (HOPs) into the lake and the degree to which these compounds are available for uptake by aquatic biota. Semipermeable membrane devices (SPMDs) have been shown to sample the readily bioavailable fraction (dissolved phase) of waterborne HOPs and in doing so provide relevant data for exposure assessment. The aim of the current study was to use SPMD-based sampling in conjunction with appropriate bioassays and chemical analysis to identify readily bioavailable HOPs in the lake. METHODS: SPMDs were constructed and deployed at three sites in the Albanian sector and three sites in the Montenegrin sector of Lake Skadar/Shkodra for 21 days. Following the dialytic recovery of target analytes and size exclusion chromatographic clean-up, aliquots of SPMD samples were subjected to GC-MS scan analysis for major components, GC-MS SIM analysis for 16 priority pollutant polycyclic aromatic hydrocarbons (PP-PAHs) and assayed for EROD-inducing, estrogenic and mutagenic potential using rainbow trout liver cells (RTL-W1), the yeast estrogen screen (YES) and the Ames Test, respectively. RESULTS AND DISCUSSION: A total of 39 compounds were tentatively identified in SPMD samples from the six sampling sites. Alkylated PAHs were the most abundant and ubiquitous compounds present along with various sterols and sterol derivatives. Numerous other compounds remain unidentified. 15 of the 16 targeted PP-PAHs were present in samples from one or more of the sampling sites indicating these compounds are both readily bioavailable and widely distributed in Lake Shkodra/Skadar. Total PP-PAH concentrations ranged between 3991 ng/SPMD and 10695 ng/SPMD. Bioassays carried out on SPMD samples revealed significant EROD-inducing and estrogenic potential at five of the six sampling sites indicating toxicologically relevant compounds are readily available for uptake by resident aquatic biota. EROD-inducing potential was positively correlated with targeted PP-PAH concentration (r2 = 0.74). However, comparison of bioassay- and analytically-derived toxicity equivalents revealed targeted PP-PAHs were responsible for less than 0.06% of the total EROD-inducing potential. CONCLUSIONS AND OUTLOOK: The combination of SPMD-based sampling with appropriate bioassays and chemical analysis provided an effective tool for the identification of environmentally relevant waterborne pollutants in Lake Shkodra/Skadar. Our results show that toxicologically relevant HOPs including EROD-inducing and potentially estrogenic compounds are widely distributed in the lake and readily available for uptake by aquatic biota. Our results also suggest that alkylated PAHs rather than parent compounds may be of greater toxicological relevance in the lake. As anthropogenic influences continue to increase, SPMD-based sampling is expected to play a central role in future research concerned with the identification, monitoring and assessment of the risk posed by HOPs to Lake Shkodra/Skadar's aquatic biota.     

Hydroxyiminodisuccinic acid (HIDS): A novel biodegradable chelating ligand for the increase of iron bioavailability and arsenic phytoextraction

The influence of biodegradable chelating ligands on arsenic and iron uptake by hydroponically grown rice seedlings (Oryza sativa L.) was investigated. Even though the growth solution contained sufficient Fe, the growth of rice seedlings gradually decreased up to 76% with the increase of pH of the solution from 7 to 11. Iron forms insoluble ferric hydroxide complexes at neutral or alkaline pH in oxic condition. Chelating ligands produce soluble ‘Fe–ligand complex’ which assist Fe uptake in plants. The biodegradable chelating ligand hydroxyiminodisuccinic acid (HIDS) was more efficient then those of ethylenediaminetetraacetic acid (EDTA), ethylenediaminedisuccinic acid (EDDS), and iminodisuccinic acid (IDS) in the increase of Fe uptake and growth of rice seedling. A total of 79 ± 20, 87 ± 6, 116 ± 15, and 63 ± 18 mg dry biomass of rice seedlings were produced with the addition of 0.5 mM of EDDS, EDTA, HIDS, and IDS in the nutrient solution, respectively. The Fe concentrations in rice tissues were 117 ± 15, 82 ± 8, 167 ± 25, and 118 ± 22 μmol g⁻¹ dry weights when 0.25 mM of EDDS, EDTA, HIDS, and IDS were added to the nutrient solution, respectively. Most of the Fe accumulated in rice tissues was stored in roots after the addition of chelating ligands in the solution. The results indicate that the HIDS would be a potential alternative to environmentally persistent EDTA for the increase of Fe uptake and plant growth. The HIDS also increased As uptake in rice root though its translocation from root to shoot was not augmented. This study reports HIDS for the first time as a promising chelating ligand for the enhancement of Fe bioavailability and As phytoextraction.     

Surface applied water treatment residuals affect bioavailable phosphorus losses in Florida sands

Water treatment residuals (WTR) can reduce runoff P loss and surface co-application of P-sources and WTR is a practical way of land applying the residuals. In a rainfall simulation study, we evaluated the effects of surface co-applied P-sources and an Al-WTR on runoff and leacheate bioavailable P (BAP) losses from a Florida sand. Four P-sources, namely poultry manure, Boca Raton biosolids (high water-soluble P), Pompano biosolids (moderate water-soluble P), and triple super phosphate (TSP) were surface applied at 56 and 224kgPha(-1) (by weight) to represent low and high soil P loads typical of P- and N-based amendments rates. The treatments further received surface applied WTR at 0 or 10gWTRkg(-1) soil. BAP loss masses were greater in leachate (16.4-536mg) than in runoff (0.91-46mg), but were reduced in runoff and leachate by surface applied WTR. Masses of total BAP lost in the presence of surface applied WTR were less than approximately 75% of BAP losses in the absence of WTR. Total BAP losses from each of the organic sources applied at N-based rates were not greater than P loss from TSP applied at a P-based rate. The BAP loss at the N-based rate of moderate water-soluble P-source (Pompano biosolids) was not greater than BAP losses at the P-based rates of other organic sources tested. The hazards of excess P from applying organic P-sources at N-based rates are not greater than observed at P-based rates of mineral fertilizer. Results suggest that management of the environmental P hazards associated with N-based rates of organic materials in Florida sands is possible by either applying P-sources with WTR or using a moderate water-soluble P-source.     

Multi-element analysis of road-deposited sediment in an urban drainage basin, Honolulu, Hawaii

Road-deposited sediment (RDS) and its associated contaminant load play a critical role in degrading receiving water bodies. Few quantitative multi-element RDS studies exist, and there are none from Hawaii. This lack of baseline data combined with concerns with high concentrations of Pb and Cu in fish and enrichment of Cu, Pb and Zn in bed sediments from Manoa Stream, Hawaii, lead to a detailed characterization of RDSs in Manoa basin. Data for a total analysis of 23 elements using inductively coupled plasma atomic-emission spectrometry and instrumental neutron activation analysis and 16 elements using a 0.5 M HCl partial leach are presented for RDSs and background soils. Concentration data, comparisons with environmental guidelines, and concentration enrichment ratios (CERs) all indicate that RDS in Manoa has a significant degree of anthropogenic pollution. The most environmentally important elements were Pb, Sb and Zn. Concentrations of these elements, primarily vehicle contributed, compare favorably with those from other studies of RDS. The high mean concentration of Pb (151 mg/kg) compared to background soils (13 mg/kg) indicates remobilization of Pb previously stored in soils and transported to road surfaces by water erosion processes. The higher Pb CER(Total) in RDSs compared to bed sediments from Manoa Stream suggests a potential link via ubiquitous storm drains and subsequent dilution with less contaminated fluvial sediments. Data from the HCl leach also support Pb and Zn as having significant anthropogenic signals, and Cu having a moderate signal. These data indicate that RDSs in Manoa basin are generally contaminated with certain potentially toxic elements and the legacy of past use of leaded gasoline is still a concern in this urban drainage system.     

Estimating risk at a Superfund site using passive sampling devices as biological surrogates in human health risk models

Passive sampling devices (PSDs) sequester the freely dissolved fraction of lipophilic contaminants, mimicking passive chemical uptake and accumulation by biomembranes and lipid tissues. Public Health Assessments that inform the public about health risks from exposure to contaminants through consumption of resident fish are generally based on tissue data, which can be difficult to obtain and requires destructive sampling. The purpose of this study is to apply PSD data in a Public Health Assessment to demonstrate that PSDs can be used as a biological surrogate to evaluate potential human health risks and elucidate spatio-temporal variations in risk. PSDs were used to measure polycyclic aromatic hydrocarbons (PAHs) in the Willamette River; upriver, downriver and within the Portland Harbor Superfund megasite for 3 years during wet and dry seasons. Based on an existing Public Health Assessment for this area, concentrations of PAHs in PSDs were substituted for fish tissue concentrations. PSD measured PAH concentrations captured the magnitude, range and variability of PAH concentrations reported for fish/shellfish from Portland Harbor. Using PSD results in place of fish data revealed an unacceptable risk level for cancer in all seasons but no unacceptable risk for non-cancer endpoints. Estimated cancer risk varied by several orders of magnitude based on season and location. Sites near coal tar contamination demonstrated the highest risk, particularly during the dry season and remediation activities. Incorporating PSD data into Public Health Assessments provides specific spatial and temporal contaminant exposure information that can assist public health professionals in evaluating human health risks.     

A Daily Time Series Analysis of StreamWater Phosphorus Concentrations Along an Urban to Forest Gradient

During a 1-year period, we sampled stream water total phosphorus (TP) concentrations daily and soluble reactive phosphorus (SRP) concentrations weekly in four Seattle area streams spanning a gradient of forested to urban-dominated land cover. The objective of this study was to develop time series models describing stream water phosphorus concentration dependence on seasonal variation in stream base flows, short-term flow fluctuations, antecedent flow conditions, and rainfall. Stream water SRP concentrations varied on average by ±18% or ±5.7 μg/L from one week to another, whereas TP varied ±48% or ±32.5 μg/L from one week to another. On average, SRP constituted about 47% of TP. Stream water SRP concentrations followed a simple sine-wave annual cycle with high concentrations during the low-flow summer period and low concentrations during the high-flow winter period in three of the four study sites. These trends are probably due to seasonal variation in the relative contributions of groundwater and subsurface flows to stream flow. In forested Issaquah Creek, SRP concentrations were relatively constant throughout the year except during the fall, when a major salmon spawning run occurred in the stream and SRP concentrations increased markedly. Stream water SRP concentrations were statistically unrelated to short-term flow fluctuations, antecedent flow conditions, or rainfall in each of the study streams. Stream water TP concentrations are highly variable and strongly influenced by short-term flow fluctuations. Each of the processes assessed had statistically significant correlations with TP concentrations, with seasonal base flow being the strongest, followed by antecedent flow conditions, short-term flow fluctuations, and rainfall. Times series models for each individual stream were able to predict ∼70% of the variability in the SRP annual cycle in three of the four streams (r² = 0.57–0.81), whereas individual TP models explained ∼50% of the annual cycle in all streams (r² = 0.39–0.59). Overall, time series models for SRP and TP dynamics explained 82% and 76% of the variability for these variables, respectively. Our results indicate that SRP, the most biologically available and therefore most important phosphorus fraction, has simpler and easier-to-predict seasonal and weekly dynamics.