Contribution of nitrogen sources to streams in mixed-use watershed varies seasonally in a temperate region

The Beiyun river flows through a hot spot region of Beijing-Tianjin-Hebei in China that serves a majority of occupants. However, the region experiences severe nitrate pollution, posing a threat to human health due to inadequate self-purification capacity. In that context, there is an urgent need to assess nitrate levels in this region. Herein, we used δ¹⁵N-NO₃, δ¹⁸O-NO₃ isotopes analysis, and stable isotope analysis model to evaluate the nitrate source apportionment in the Beiyun river. A meta-analysis was then used to compare the potential similarity of nitrate sources among the Beiyun riverine watershed and other watersheds. Results of nitrate source apportionment revealed that nitrate originated from the manure and sewage (contribution rate: 89.6%), soil nitrogen (5.9%), and nitrogen fertilizer (3.9%) in the wet season. While in the dry season, nitrate mainly originated from manure and sewage (91.6%). Furthermore, different land-use types exhibited distinct nitrate compositions. Nitrate in urban and suburban areas mostly was traced from manure and sewage (90.5% and 78.8%, respectively). Notably, the different nitrate contribution in the rural-urban fringe and plant-covered areas were manure and sewage (44.3% and 32.8%), soil nitrogen (26.9% and 35.7%), nitrogen fertilizer (23.5% and 29.4%), and atmospheric deposition (5.3% and 2.0%). Through a meta-analysis, we found nitrogen fertilizer, soil nitrogen, and manure and sewage as the main nitrate sources in the Beiyun riverine watershed or the other similar complexed watersheds in the temperate regions. Thus, this study provides a scientific basis for nitrate source apportionment and nitrate pollution preventive management in watersheds with complexed land-use types in temperate regions.

     

Binding of triclosan to human serum albumin: insight into the molecular toxicity of emerging contaminant

Purpose

The interaction between triclosan (TCS) and human serum albumin (HSA) was investigated in order to obtain the binding mechanism, binding constant, the type of binding force, the binding distance between the donor and acceptor, and the effect of TCS on the conformation change of HSA.

Methods

A HSA solution was added to the quartz cell and then titrated by successive addition of TCS. The fluorescence quenching spectra and synchronous spectra were recorded with the excitation and emission slits of the passage of band set at 10 and 20 nm. Three-dimensional fluorescence spectra of HSA were recorded before and after the addition of TCS. The capillary electrophoresis was conducted with the pressure injection mode at 0.5 psi for 5 s, separation under 25 kV, and detection at 214 nm.

Results

Fluorescence data indicated the fluorescence quenching of HSA by TCS was static quenching, and the quenching constants (K _a ) were 1.14?×?10⁵, 8.75?×?10⁴, 6.67?×?10⁴, and 5.00?×?10⁴ at 293, 298, 303, and 309 K, respectively. The thermodynamic parameters, enthalpy change (??H) and entropy change (??S) for the interaction were calculated to be ?37.9 kJ mol^?1 and 32.6 J?mol^?1 K^?1. The binding distance between TCS and tryptophan residues of HSA was obtained to be 1.81 nm according to F??rster nonradioactive energy transfer theory. The UV-Vis absorption spectroscopy, the synchronous fluorescence spectroscopy, three-dimensional fluorescence spectroscopy, and circular dichroism spectroscopy revealed the alterations of HSA secondary structure in the presence of TCS. Finally, the interaction between TCS and HSA was further confirmed by capillary electrophoresis.

Conclusions

TCS was bound to HSA to form the TCS-HSA complex, with the binding distance of 1.81 nm. Hydrophobic interaction and hydrogen bond were dominated in the binding. TCS could change the secondary conformation of HSA. This work provides an insight into noncovalent interaction between emerging pollutants and protein, helping to elucidate the toxic mechanism of such pollutants.     

Organic contaminant loads into the Western Mediterranean Sea: estimate of Ebro River inputs

Annual input estimates for several organic contaminants from the Ebro River into the Northwestern Mediterranean Sea were carried out on the basis of monthly sampling from November 2002 to October 2003. Some organochlorine compounds (DDT and its degradation products, DDD and DDE, PCBs (9 congeners), HCB and gamma-HCH) were selected due to their reported occurrence in the river. Furthermore, some polar pesticides used in the Ebro Delta were also determined (atrazine, simazine, diazinon, fenitrothion and molinate). Concentrations ranged from 0.4 to 19.5 ng l(-1) for the organochlorine compounds (sum of particulate and dissolved phases) and from not detected (ND) to 170 ng l(-1) for the more polar pesticides, which were only found in the dissolved phase. The sum of PCB congeners (mean 8.9 ng l(-1)) showed the highest concentrations among the organochlorine compounds and atrazine (mean 82 ng l(-1)) among the polar pesticides. Based on the contaminant concentrations and on hydrological data, contaminant discharges into the sea were estimated amounting in total to 167 and 1,258 kg year(-1) of organochlorine compounds and polar pesticides, respectively. Furthermore, it was observed that PCBs, DDTs and HCB inputs were basically influenced by spate periods due to an increase in suspended particulate matter associated to runoff and sediment resuspension. Whereas for more water soluble contaminants, such as the agrochemicals, their seasonal use had a higher incidence in contaminant fluxes. Bulk chemical parameters such as SPM, DOC, POC, %OC, %ON and C/N ratio provided additional information on the organic matter sources. This provides a better understanding of the temporal variability of the contaminant concentrations.     

Persistence and runoff losses of 3 herbicides and chlorpyrifos from a corn field in the Lake Balaton watershed of Hungary

Corn is intensively cultivated in western Hungary in the basin of Lake Balaton, one of the most important water resources in eastern Europe. Pesticide runoff was measured in 1996 and 1997 from a typical corn field near Zalaegerszeg, Hungary, which drains into the Zala River, an important water source of Lake Balaton. Three herbicides, namely atrazine, acetochlor, and propizochlor, and the insecticide chlorpyrifos were applied to bare soil in a field with 5% slope and soil and runoff water pesticide concentrations were monitored. In 1997, a rainfall-runoff simulation experiment was conducted on a small sub-plot in order to measure pesticide runoff under reasonable worst-case conditions. Under natural rainfall almost all losses occurred in a large runoff event in 1996 one month after application in which 3% of atrazine and 1% of acetochlor was transported off the field. Propizochlor and chlorpyrifos losses in the same event were much lower: 0.2% and <0.01%, respectively, because of these chemicals' shorter persistence times in near-surface soil. The rainfall simulation produced only trace amounts of losses even though 4.1 cm was applied in 2 hours; the soil was extremely dry and only 0.2 cm runoff occurred containing less than 0.01% of all chemicals applied. The results suggest that intensive use of corn herbicides, which have been found to result in widespread contamination of water resources elsewhere, may be expected to have the same impact in the Balaton watershed depending on the amounts and intensities used in the basin.     

BETR North America: a regionally segmented multimedia contaminant fate model for North America

We present the Berkeley-Trent North American contaminant fate model (BETR North America), a regionally segmented multimedia contaminant fate model based on the fugacity concept. The model is built on a framework that links contaminant fate models of individual regions, and is generally applicable to large, spatially heterogeneous areas. The North American environment is modeled as 24 ecological regions, within each region contaminant fate is described using a 7 compartment multimedia fugacity model including a vertically segmented atmosphere, freshwater, freshwater sediment, soil, coastal water and vegetation compartments. Inter-regional transport of contaminants in the atmosphere, freshwater and coastal water is described using a database of hydrological and meteorological data compiled with Geographical Information Systems (GIS) techniques. Steady-state and dynamic solutions to the 168 mass balance equations that make up the linked model for North America are discussed, and an illustrative case study of toxaphene transport from the southern United States to the Great Lakes Basin is presented. Regionally segmented models such as BETR North America can provide a critical link between evaluative models of long-range transport potential and contaminant concentrations observed in remote regions. The continent-scale mass balance calculated by the model provides a sound basis for evaluating long-range transport potential of organic pollutants, and formulation of continent-scale management and regulatory strategies for chemicals.     

Sublethal contaminant exposure alters behavior in a common insect: Important implications for trophic transfer

This study examined the effects of sub-lethal exposure of the ubiquitous pesticide malathion on the behavior of the model orthopteran species, the house cricket (Acheta domesticus). Increasing concentrations of malathion caused male crickets to increase periods of non-directional movement, such as twitching and grooming, directional movement, and to seek out shelter less. These are all behavioral alterations that may increase the cricket's chances of being preyed upon, and thus have the potential for serious ecological consequences through trophic transfer. This study also revealed that female crickets appeared to be less affected by malathion than their male conspecifics, indicating a potential sex-bias in both susceptibility and possible predator attack.     

Source term characterisation using concentration trends and geochemical associations of Pb and Zn in river sediments in the vicinity of a disused mine site: Implications for contaminant metal dispersion processes

River sediment at a disused lead-zinc mine was analysed to provide an understanding of the chemical nature of the source term for contaminated sediment exported from the site. Changes in concentration and geochemical associations of Pb and Zn were measured using aqua regia digestion and the BCR sequential extraction procedure. Sediment in the immediate vicinity of the mine was highly contaminated with Pb (max. c. 11,000 mg kg⁻¹) and Zn (max. c. 30,000 mg kg⁻¹), but these values declined rapidly within 1 km of the mine due to dilution and hydraulic sorting. Lead fractionation changed from being predominantly in the reducible fraction to being in the acetic acid-extractable fraction, whereas Zn was predominantly in the residual fraction. This material is transported as fine sediment in the river system.     

Supporting evidences for vegetation-enhanced stormwater infiltration in bioretention systems: a comprehensive review

Environmental Science and Pollution Research - Stormwater mitigation efficiency of bioretention systems relies for a large part on their capacity to infiltrate rapidly received runoff. Within this...     

A PCE groundwater plume discharging to a river: influence of the streambed and near-river zone on contaminant distributions

An investigation of a tetrachloroethene (PCE) groundwater plume originating at a dry cleaning facility on a sand aquifer and discharging to a river showed that the near-river zone strongly modified the distribution, concentration, and composition of the plume prior to discharging into the surface water. The plume, streambed concentration, and hydrogeology were extensively characterized using the Waterloo profiler, mini-profiler, conventional and driveable multilevel samplers (MLS), Ground Penetrating Radar (GPR) surveys, streambed temperature mapping (to identify discharge zones), drivepoint piezometers, and soil coring and testing. The plume observed in the shallow streambed deposits was significantly different from what would have been predicted based on the characteristics of the upgradient plume. Spatial and temporal variations in the plume entering the near-river zone contributed to the complex contaminant distribution observed in the streambed where concentrations varied by factors of 100 to 5000 over lateral distances of less than 1 to 3.5 m. Low hydraulic conductivity semi-confining deposits and geological heterogeneities at depth below the streambed controlled the pattern of groundwater discharge through the streambed and influenced where the plume discharged into the river (even causing the plume to spread out over the full width of the streambed at some locations). The most important effect of the near-river zone on the plume was the extensive anaerobic biodegradation that occurred in the top 2.5 m of the streambed, even though essentially no biodegradation of the PCE plume was observed in the upgradient aquifer. Approximately 54% of the area of the plume in the streambed consisted solely of PCE transformation products, primarily cis-1,2-dichloroethene (cDCE) and vinyl chloride (VC). High concentrations in the interstitial water of the streambed did not correspond to high groundwater-discharge zones, but instead occurred in low discharge zones and are likely sorbed or retarded remnants of past high-concentration plume discharges. The high-concentration areas (up to 5529 microg/l of total volatile organics) in the streambed are of ecological concern and represent potential adverse exposure locations for benthic and hyporheic zone aquatic life, but the effect of these exposures on the overall health of the river has yet to be determined. Even if the upgradient source of PCE is remediated and additional PCE is prevented from reaching the streambed, the high-concentration deposits in the streambed will likely take decades to hundreds of years to flush completely clean under natural conditions because these areas have low vertical groundwater flow velocities and high retardation factors. Despite high concentrations of contaminants in the streambed, PCE was detected in the surface water only rarely due to rapid dilution in the river and no cDCE or VC was detected. Neither the sampling of surface water nor the sampling of the groundwater from the aquifer immediately adjacent to the river gave an accurate indication of the high concentrations of PCE biodegradation products present in the streambed. Sampling of the interstitial water of the shallow streambed deposits is necessary to accurately characterize the nature of plumes discharging to rivers.     

Towards a more appropriate water based extraction for the assessment of organic contaminant availability

This study correlated extractabilities of 37 d aged phenanthrene residues in four dissimilar soils with the fraction that was available for earthworm (Lumbricus rubellus) accumulation and microorganism (Pseudomonas sp.) mineralisation. Extractability was determined using two established techniques, namely, (1) a water based extraction using CO(2) equilibrated water and (2) an aqueous based hydroxypropyl-beta-cyclodextrin (HPCD) extraction. Results showed no relationship between earthworm accumulation and phenanthrene extractability using either HPCD (r(2)=0.07; slope=-4.76; n=5) or the water based extraction (r(2)=0.31; slope=-5.34; n=5). Earthworm accumulation was overestimated by both techniques. In contrast, the fraction of phenanthrene extractable using both the HPCD technique and the water based extraction correlated strongly with microbial mineralisation. However, the slopes of these linear relationships were 0.48 (r(2)=0.96; n=10), and 0.99 (r(2)=0.88; n=10) for the water based extraction and HPCD, respectively. Thus, the HPCD extraction provided values that were numerically close to the mineralisation values, whilst the water based extraction values were approximately half the mineralisation values. It is submitted that HPCD extraction provided an appropriate method of assessing the fraction of contaminant available for microbial mineralisation in these dissimilar soils.     

土壤渗滤处理系统运行控制的模拟研究

通过建立地下水数学模型,回答了土壤渗滤工程运行控制中的两个难点问题:(1)工程运行水力负荷.当工程地块周边存在河流时,河流水位低时,有助于增加水力负荷,反之则降低水力负荷;实际土壤运行面积的增加和独立运行单元之间的间距增加也能够增加工程运行水力负荷.(2)地下水水质监测井的优化布设.模拟工程运行后地下水水质空间分布特征,在地下水水质最不利的位置和其他特别关注的位置布置监测井,从而能够以具有典型代表性且数目较少的监测井达到准确评估工程对地下水水质影响的目的.     

A simulation-based method to develop strategies for nitrogen pollution control in a creek watershed with sparse data

Environmental Science and Pollution Research - Well-defined targets for nitrogen (N) release into the local environment are essential for water management in creeks, but difficulties often arise...     

Rapid transport from the surface to wells in fractured rock: a unique infiltration tracer experiment

A unique infiltration tracer experiment was performed whereby a fluorescent dye was applied to the land surface in an agricultural field, near Perth, Ontario, Canada, to simulate the transport of solutes to two pumped monitoring wells drilled into the granitic gneiss aquifer. This experiment, interpreted using the discrete-fracture capability of the numerical model HydroGeoSphere, showed that solute transport from the surface through thin soil (less than 2m) to wells in fractured bedrock can be extremely rapid (on the order of hours). Also, it was demonstrated that maximum concentrations of contaminants originating from the ground surface will not necessarily be the highest in the shallow aquifer horizon. These are important considerations for both private and government-owned drinking water systems that draw water from shallow fractured bedrock aquifers. This research illustrates the extreme importance of protecting drinking water at the source.     

Biosolids-amended soils: Part II. Chemical lability as a measure of contaminant bioaccessability.

Biosolids recycling by amending agricultural soils has increased significantly over the last few decades. The presence of contaminants in small, bioavailable quantities has generated concerns about health threats resulting from accumulation of potential toxins in the food chain. In this study, land application of biosolids was evaluated for environmental risk. Chemical lability tests for metals were used for the test soils and included analyses for water soluble, exchangeable, and metals extractable by the physiologically based extraction test. Chemical extractions detected slight increases in labile metal concentrations for many of the treated soils, particularly those receiving long-term applications of 5 years or more. Significantly higher metal concentrations were observed in the soils that had been exposed to biosolids before the U.S. Environmental Protection Agency (Washington, D.C.) 503 Rule (U.S. EPA, 2004) was implemented.     

Surfactant-induced mobilisation of trace metals from estuarine sediment: implications for contaminant bioaccessibility and remediation

The mobilisation of metals (Al, Fe, Cd, Cu, Mn, Ni, Pb, Sn, Zn) from contaminated estuarine sediment has been examined using commercially available surfactants. Metal release by the anionic surfactant, sodium dodecyl sulphate (SDS), increased with increasing amphiphile concentration up to and above its critical micelle concentration (CMC). Metal mobilisation by the bile acid salt, sodium taurocholate, and the nonionic surfactant, Triton X-100, however, did not vary with amphiphile concentration. SDS was the most efficient surfactant in mobilising metals from the sample, and Cd, Cu and Ni were released to the greatest extents (12-18% of total metal at [SDS] > CMC). Metal mobilisation appeared to proceed via complexation with anionic amphiphiles and denudation of hydrophobic host phases. Surfactants may play an important role in the solubilisation of metals in the digestive environment of deposit-feeding animals and, potentially, in the remediation of metal-contaminated soil and sediment.     

Contribution of harbour activities to levels of particulate matter in a harbour area: Hada Project-Tarragona Spain

The present study seeks to estimate the impact of harbour activities on PM10 levels based on a complete chemical characterisation of 90 PM10 samples periodically collected between September 2004 and September 2005 in the harbour of Tarragona as part of the HADA (LIFE Program EC) project. Interpretation of the time series of major and trace PM10 components allowed us to identify peaks of PM10 components related to the activities in the harbour. A factor analysis of PM10 enabled us to identify the crustal, traffic, secondary and sea spray sources, and one other source related to the re-suspension of materials handled in the harbour. The multi-linear regression analysis demonstrated a high anthropogenic contribution (62%) for PM10 at the harbour, mainly related to traffic (34% of PM10). Comparison with an earlier study, using the same methodology, at an urban background monitoring station in Tarragona, showed a good correlation for the annual average concentrations of most PM10 components at the two stations. At the harbour higher concentrations were obtained for tracers (P and Mn, and V and Ni in a lesser extent) of some mineral bulk cargo materials. Re-suspension of loose materials by means of wind and/or traffic was identified as one of the major contributors to PM10 in the harbour. Abatement strategies designed to reduce levels of PM10 in the harbour and nearby areas are provided.     

Implications of climate change for the stomatal flux of ozone: a case study for winter wheat

Climate change factors such as elevated CO2 concentrations, warming and changes in precipitation affect the stomatal flux of ozone (O3) into leaves directly or indirectly by altering the stomatal conductance, atmospheric O3 concentrations, frequency and extent of pollution episodes and length of the growing season. Results of a case study for winter wheat indicate that in a future climate the exceedance of the flux-based critical level of O3 might be reduced across Europe, even when taking into account an increase in tropospheric background O3 concentration. In contrast, the exceedance of the concentration-based critical level of O3 will increase with the projected increase in tropospheric background O3 concentration. The influence of climate change should be considered when predicting the future effects of O3 on vegetation. There is a clear need for multi-factorial, open-air experiments to provide more realistic information for O3 flux-effect modelling in a future climate.     

Passive water sampling for polynuclear aromatic hydrocarbons using lipidcontaining semipermeable membrane devices (SPMDs): Application to contaminant residence times

Lipid-containing semipermeable membrane devices are applied to the quantitative determination of the persistence of polynuclear aromatic hydrocarbons (PAH) in an irrigation water canal, a representative waterway. The uniform and reproducible sampling of the USGS design of lipid-containing SPMDs is exploited to measure PAH half-lives without requiring calculation of water concentrations. The trend in calculated PAH half-lives agrees with that expected if volatilization is a significant mechanism for loss from the canal with more volatile PAHs having shorter half-lives. The higher persistence of phenanthrene compared to anthracene is consistent with the greater stability of phenanthrene and suggests, with other physicochemical evidence, that other (reactive) mechanisms may be involved. The results of this study demonstrate the feasibility of the SPMD method for the measurement of residence times in aquatic and other compartments. Such information is essential for quantifying contaminant behavior in the environment and providing insights into contaminant fate.