Quantifying stream-aquifer interactions through the analysis of remotely sensed thermographic profiles and in situ temperature histories

The interaction between surface and subsurface waters through hyporheic exchange and baseflow is critical to maintaining ecological health in streams. During warm periods, groundwater-surface water interactions have two primary effects on stream temperature: (1) cool groundwater discharging as baseflow lowers stream temperature and (2) hyporheic exchange buffers diurnal stream temperature variations. We demonstrate, for the first time, how high-resolution, remotely sensed forward-looking infrared (FLIR) images and instream temperature data can be used to quantify detailed spatial patterns of groundwater discharge to a 1.7 km reach of Cottonwood Creek in Plumas National Forest, CA. We quantifythe individual effects of baseflow and hyporheic exchange on stream temperatures by simulating the stream energy budget under different conceptual models of the stream-aquifer interaction. Observed spatial and temporal patterns of stream temperature are consistent with an increase in baseflow and hyporheic exchange within the middle, restored stream reach when compared to groundwater fluxes in the surrounding, unrestored reaches. One implication is that pond and plug stream restoration may improve the aquatic habitat by depressing maximum stream temperatures by > 3 degrees C (K).     

Occurrence of iodinated X-ray contrast media and their biotransformation products in the urban water cycle

A LC tandem MS method was developed for the simultaneous determination of four iodinated X-ray contrast media (ICM) and 46 ICM biotransformation products (TPs) in raw and treated wastewater, surface water, groundwater, and drinking water. Recoveries ranged from 70% to 130%, and limits of quantification (LOQ) varied between 1 ng/L and 3 ng/L for surface water, groundwater and drinking water, and between 10 ng/L and 30 ng/L for wastewater. In a conventional wastewater treatment plant, iohexol, iomeprol, and iopromide were transformed to >80%, while iopamidol was transformed to 35%. In total, 26 TPs were detected above their LOQ in WWTP effluents. A significant change in the pattern of ICM TPs was observed after bank filtration and groundwater infiltration under aerobic conditions. Predominately, these TPs are formed at the end of the microbial transformation pathways in batch experiments with soil and sediment. These polar ICM TPs, such as iohexol TP599, iomeprol TP643, iopromide TP701A, and iopromide TP643, were not or only partially removed during drinking water treatment. As a consequence, several ICM TPs were detected in drinking water, at concentration levels exceeding 100 ng/L, with a maximum of 500 ng/L for iomeprol TP687.     

Indicators for the exposure assessment of transformation products of organic micropollutants

Environmental transformation products of organic micropollutants have the potential to be similarly or even more mobile, persistent, ortoxic than their parent compounds. They should, therefore, be included in chemical hazard and risk assessment procedures as well as in the assessment of soil and water quality. To fulfill this requirement most efficiently, screening approaches that select relevant transformation products for detailed assessment are needed. This paper presents two process-based multimedia, multispecies models that allow us to quantitatively estimate the environmental fate of transformation products. The resulting exposure patterns are assessed with two indicators: joint persistence (JP), which describes the temporal extent of environmental exposure to a parent compound and its transformation products, and the predicted relative aquatic concentrations (RAC), which estimate the relative concentrations of parent compounds and their transformation products in surface water bodies. As a case study, JP and RAC are calculated for 16 pesticides and their relevant transformation products. The results for the JP indicator confirm the importance of considering transformation products in the assessment of overall persistence; for example, in the context of PBT assessments. Comparison of RAC results with monitoring data on herbicides and their transformation products shows the suitability of our approach for estimating relative concentrations in surface water, and as a consequence, its usefulness in identifying transformation products for future water quality monitoring programs. Transformation products of triketones and other highly used acidic herbicides are specifically identified as targets.     

Transformation of the X-ray contrast medium iopromide in soil and biological wastewater treatment

In water/soil systems, the iodinated contrast medium iopromide was quantitatively biotransformed into several transformation products (TPs). Twelve TPs were identified via HPLC-UV and LC tandem MS. The chemical structures of the TPs were elucidated via fragmentation in MS2 and MS3 of LC tandem MS with a linear ion trap and 1H and 13C NMR analyses. All TPs exhibited transformations at the side chains containing either carboxylic moieties and/or primary and secondary amide moieties, while the triiodoisophthalic acid structure remained unaltered. A transformation pathway was proposed based on the sequence of TP formation in aerobic batch experiments. Additionally, the occurrence of iopromide TPs was investigated in native water samples. All TPs identified were found in municipal WWTP effluents because of their formation during biological wastewater treatment with maximum concentrations of up to 3.7 +/- 0.9 microg/L (TP 819). Predominantly, those TPs were present at higher concentrations in WWTP effluents which were formed at the beginning of the transformation pathway. Furthermore, four TPs formed at the end of the transformation pathway (TP 759, 701A/B, and 643) were also found in bank filtrate up to 0.050 microg/L and in groundwater of an wastewater irrigation area up to 4.6 microg/L.     

Probabilistic ecological risk assessment of 1,2,4-trichlorobenzene at a former industrial contaminated site

Measured concentrations of 1,2,4-trichlorobenzene (1,2,4-TCB) in soil and groundwater detected in an industrial contaminated site were used to test several probabilistic options for refining site-specific ecological risks assessment, ranging from comparison of single effects and exposure values through comparison of probabilistic distributions for exposure and effects to the use of distribution based quotients (DBQs) obtained through Monte Carlo simulations. The results of the deterministic approach, which suggest that risk exceeds a level of concern for soil organisms, were influenced mainly by the presence of hot spots reaching concentrations able to affect acutely a large proportion of species, while the large majority of the area presents 1,2,4-TCB concentrations below those reported as toxic. Ground-(pore)water concentrations were compared with aquatic ecotoxicity data in orderto obtain an estimation of the potential risk for aquifers and streams in the adjacent area as well as for soil-dwelling organisms exposed via pore water. In this case, the risk is distributed over a large proportion of the site, while the local risk of hot spots was low, showing that risk characterization based exclusively on soil concentrations might be insufficient.     

Input dynamics and fate in surface water of the herbicide metolachlor and of its highly mobile transformation product metolachlor

A large number of herbicide transformation products has been detected in surface waters and groundwaters of agricultural areas, often even in higher concentrations and more frequently than their parent compounds. However, their input dynamics and fate in surface waters are still rather poorly understood. This study compares the aquatic fate, concentration levels, and dynamics of the transformation product metolachlor ethanesulfonic acid (metolachlor ESA) and its parent compound metolachlor, an often-used corn herbicide. To this end, laboratory photolysis studies were combined with highly temporally resolved concentration measurements and lake mass balance modeling in the study area of Lake Greifensee (Switzerland). It is found that the two compounds show distinctly different concentration dynamics in the lake tributaries. Concentration-discharge relationships for metolachlor ESA in the main tributary showed a high baseflow concentration and increasing discharge dependence during harvest season, whereas baseflow concentrations of metolachlor were negligible and the discharge dependence was restricted to the period immediately following application. From this it was estimated that 70% of the yearly load of metolachlor ESA to the lake was due to groundwater recharge, whereas, for metolachlor, the bigger part of the load, 50-80%, stemmed from event-driven runoff. Lake mass balance modeling showed that the input dynamics of metolachlor and metolachlor ESA are reflected in their concentration dynamics in the lake's epilimnion and that both compounds show a similar fate in the epilimnion of Lake Greifensee during the summer months with half-lives on the order of 100-200 days, attributable to photolysis and another loss process of similar magnitude, potentially biodegradation. The behavior of metolachlor ESA can likely be generalized to other persistent and highly mobile transformation products. In the future, this distinctly different behavior of mobile pesticide transformation products should find a more appropriate reflection in exposure models used in chemical risk assessment and in pesticide risk management.     

Surface complexation of ferrous iron and carbonate on ferrihydrite and the mobilization of arsenic

Surface complexation models are commonly used to predict the mobility of trace metals in aquifers. For arsenic in groundwater, surface complexation models cannot be used because the database is incomplete. Both carbonate and ferrous iron are often present at a high concentration in groundwater and will influence the sorption of arsenic, but the surface complexation constants are absent in the database of Dzombak and Morel. This paper presents the surface complexation constants for carbonate and ferrous iron on ferrihydrite as derived for the double-layer model. For ferrous iron the constants were obtained from published data supplemented by new experiments to determine the sorption on the strong sites of ferrihydrite. For carbonate the constants were derived from experiments by Zachara et al., who employed relatively low concentrations of carbonate. The double-layer model, optimized for low concentrations, was tested against sorption experiments of carbonate on goethite at higher concentration by Villalobos and Leckie, and reasonable agreement was found. Sorption was also estimated using linear free energy relations (LFER), and results compared well with our derived constants. Model calculations confirm that sorption of particularly carbonate at common soil and groundwater concentrations reduces the sorption capacity of arsenic on ferrihydrite significantly. The displacing effect of carbonate on sorbed arsenate and arsenite has been overlooked in many studies. It may be an important cause for the high concentrations of arsenic in groundwater in Bangladesh. Sediments containing high amounts of sorbed arsenic are deposited in surface water with low carbonate concentrations. Subsequently the sediments become exposed to groundwater with a high dissolved carbonate content, and arsenic is mobilized by displacement from the sediment surface.     

PhetoFate: a new approach in accounting for the contribution of indirect photolysis of pesticides and pharmaceuticals in surface waters

A new approach was developed to account for the contribution of indirect photolysis of pesticides and pharmaceuticals in which laboratory test conditions are similar to those prevalent in the aqueous environment. Rates of photolysis as a function of water composition were investigated for several aquatic contaminants. Using the laboratory-based test system, PhotoFate, the dependence of phototransformation rates on concentrations of natural water constituents that are radical producers and scavengers (nitrate, colored dissolved organic matter, bicarbonate) was studied. Mean half-lives of the model compounds in the presence of water constituents were compared to their direct photolysis half-lives to assess the contribution of photosensitized reactions to their fate in surface waters. Reactions mediated by .OH were predominant in waters with high nitrate concentrations. Colored dissolved organic matter (cDOM) acted mainly as a radiation filter and had a more important role in scavenging radicals than in their production. However, in low nitrate waters, the contribution of cDOM-derived reactive intermediates to the degradation of parent compounds became more apparent     

New ecotoxicological model to simulate survival of aquatic invertebrates after exposure to fluctuating and sequential pulses of pesticides

Aquatic nontarget organisms are exposed to fluctuating concentrations or sequential pulses of contaminants, so we need to predict effects resulting from such patterns of exposure. We present a process-based model, the Threshold Damage Model (TDM), that links exposure with effects and demonstrate how to simulate the survival of the aquatic invertebrate Gammarus pulex. Based on survival experiments of up to 28 days duration with three patterns of repeated exposure pulses and fluctuating concentrations of two pesticides with contrasting modes of action (pentachlorophenol and chlorpyrifos) we evaluate the new model and compare it to two approaches based on time-weighted averages. Two models, the Threshold Damage Model and the time-weighted averages fitted to pulses, are able to simulate the observed survival (mean errors 15% or less, r2 between 0.77 and 0.96). The models are discussed with respect to their theoretical base, data needs, and potential for extrapolation to different scenarios. The Threshold Damage Model is particularly useful because its parameters can be used to calculate recovery times, toxicokinetics are separated from toxicodynamics, and parameter values reflect the mode of action.     

Effects of the feedlot contaminant 17alpha-trenbolone on reproductive endocrinology of the fathead minnow

Trenbolone acetate is a growth promoter widely used for beef production in the U.S. Two biologically active metabolites of the acetate, 17beta- and 17alpha-trenbolone, are ligands of vertebrate androgen receptors and comparatively stable in the waste of treated animals. Both have been detected in surface water associated with beef feedlots, suggesting a potential risk to aquatic animals. In previous work we evaluated the effects of beta-trenbolone on reproductive endocrinology of the fathead minnow (Pimephales promelas) in a 21-day test. The purpose of the present study was to conduct a similar set of experiments with alpha-trenbolone which, based on binding to mammalian androgen receptors, was expected to be less potent than beta-trenbolone. Fecundity of the fish was significantly reduced by alpha-trenbolone with an EC50 (95% confidence interval) of 0.011 (0.007-0.016) microg/L. In females, alpha-trenbolone reduced plasma vitellogenin and steroid concentrations and also induced the production of dorsal nuptial tubercles, structures normally present only in spawning males. Overall, effects of alpha-trenbolone on the reproductive system of the fish were qualitatively and quantitatively quite similar to those caused by beta-trenbolone. Part of this similarity might arise from the fact that a substantial amount of the alpha-trenbolone appeared to be converted to beta-trenbolone by the fish. Tissue concentrations of the beta-isomer were consistently similar to or greater than concentrations of alpha-trenbolone, despite the fact that no beta-trenbolone was detected in the exposure water. The present study demonstrates the importance of considering both alpha- and beta-trenbolone in assessing the potential ecological risk of androgens associated with beef feedlot discharges.     

Reconstitution studies of pesticides and surfactants exploring the cause of estrogenic activity observed in surface waters of the san francisco bay delta

To evaluate the potential role of endocrine disruption in the decline of pelagic fishes in the San Francisco Bay Delta of California, various surface water samples were collected, extracted, and found to elicit estrogenic activity in laboratory fish. Chemical analysis of the estrogenic samples indicated 2 pesticides (bifenthrin, diuron), 2 alkyphenols (AP), and mixtures of 2 types of alkyphenol polyethoxylates (APEOs). Evaluation of estrogenic activity was further characterized by in vitro bioassays using rainbow trout hepatocytes (Oncorhynchus mykiss) and in vivo studies with Japanese medaka (Oryzias latipes). In the in vitro bioassays, hepatocytes exposed to the pesticides alone or in combination with the AP/APEO mixtures at concentrations observed in surface waters failed to show estrogenic activity (induction of vitelloginin mRNA). In the in vivo bioassays, medaka exposed to individual pesticides or to AP/APEO alone did not have elevated VTG at ambient concentrations. However, when the pesticides were combined with AP/APEOs in the 7-day exposure a significant increase in VTG was observed. Exposure to a 5-fold higher concentration of the AP/APEO mixture alone also significantly induced VTG. In contrast to earlier studies with permethrin, biotransformation of bifenthrin to estrogenic metabolites was not observed in medaka liver microsomes and cytochrome P450 was not induced with AP/APEO treatment. These results showed that mixtures of pesticides with significantly different modes of action and AP/APEOs at environmentally relevant concentrations may be associated with estrogenic activity measured in water extracts and feral fish that have been shown to be in population decline in the San Francisco Bay Delta.     

Advection dominated transport of polycyclic aromatic hydrocarbons in amended sediment caps

Typical sand caps used for sediment remediation have little sorption capacity to retard the migration of hydrophobic contaminants such as PAHs that can be mobilized by significant groundwater flow. Laboratory column experiments were performed using contaminated sediments and capping materials from a creosote contaminated USEPA Superfund site. Azoic laboratory column experiments demonstrated rapid breakthrough of lower molecular weight PAHs when groundwater seepage was simulated through a column packed with coarse sand capping material. After eight pore volumes of flow, most PAHs measured showed at least 50% of initial source pore water concentrations at the surface of 65 cm capping material. PAH concentration in the cap solids was low and comparable to background levels typically seen in urban depositional sediment, but the pore water concentrations were high. Column experiments with a peat amendment delayed PAH breakthrough. The most dramatic result was observed for caps amended with activated carbon at a dose of 2% by dry weight. PAH concentrations in the pore water of the activated carbon amended caps were 3-4 orders of magnitude lower (0.04 ± 0.02 μg/L for pyrene) than concentrations in the pore water of the source sediments (26.2 ± 5.6 μg/L for pyrene) even after several hundred pore volumes of flow. Enhancing the sorption capacity of caps with activated carbon amendment even at a lower dose of 0.2% demonstrated a significant impact on contaminant retardation suggesting consideration of active capping for field sites prone to groundwater upwelling or where thin caps are desired to minimize change in bathymetry and impacts to aquatic habitats.     

Modeling the probability of arsenic in groundwater in New England as a tool for exposure assessment

We developed a process-based model to predict the probability of arsenic exceeding 5 microg/L in drinking water wells in New England bedrock aquifers. The model is being used for exposure assessment in an epidemiologic study of bladder cancer. One important study hypothesis that may explain increased bladder cancer risk is elevated concentrations of inorganic arsenic in drinking water. In eastern New England, 20-30% of private wells exceed the arsenic drinking water standard of 10 micrograms per liter. Our predictive model significantly improves the understanding of factors associated with arsenic contamination in New England. Specific rock types, high arsenic concentrations in stream sediments, geochemical factors related to areas of Pleistocene marine inundation and proximity to intrusive granitic plutons, and hydrologic and landscape variables relating to groundwater residence time increase the probability of arsenic occurrence in groundwater. Previous studies suggest that arsenic in bedrock groundwater may be partly from past arsenical pesticide use. Variables representing historic agricultural inputs do not improve the model, indicating that this source does not significantly contribute to current arsenic concentrations. Due to the complexity of the fractured bedrock aquifers in the region, well depth and related variables also are not significant predictors.     

Coupling automated radon and carbon dioxide measurements in coastal waters

Groundwater discharge could be a major, but as yet poorly constrained, source of carbon dioxide to lakes, wetlands, rivers, estuaries, and coastal waters. We demonstrate how coupled radon ((222)Rn, a natural groundwater tracer) and pCO(2) measurements in water can be easily performed using commercially available gas analysers. Portable, automated radon and pCO(2) gas analysers were connected in series and a closed air loop was established with gas equilibration devices (GED). We experimentally assessed the advantages and disadvantages of six GED. Response times shorter than 30 min for (222)Rn and 5 min for pCO(2) were achieved. Field trials revealed significant positive correlations between (222)Rn and pCO(2) in estuarine waterways and in a mangrove tidal creek, implying that submarine groundwater discharge was a source of CO(2) to surface water. The described system can provide high resolution, high precision concentrations of both radon and pCO(2) with nearly no additional effort compared to measuring only one of these gases. Coupling automated (222)Rn and pCO(2) measurements can provide new insights into how groundwater seepage contributes to aquatic carbon budgets.     

水产品中农药残留国内外标准体系分析与检测方法研究进展

水产品作为优质膳食来源之一, 不规范使用农药行为使渔业养殖水源被污染, 水产品的质量安全面临极大的威胁。针对水产品中药物残留的监督抽检主要集中在兽药残留的检测, 但对水产品中农药残留存在监管不足的问题。本文分析了国内外水产品中农药残留限量标准的差异, 发现我国在农药数量和最大残留限量项次两方面与国际食品法典委员会相当，但与欧盟、美国、日本等其他主要贸易国家有较大差距, 特别是对法规之外且非豁免的农药的“一律限量”要求是我国食品质量安全管理的空白，这为我国完善水产品中农药最大残留限量标准制修订提供参考。同时, 本文从提取、净化、检测3个方面综述了水产品中农药残留的检测方法, 发现采用乙腈提取、QuEChERS净化的前处理方法能提高水产品中农药残留的检测效率。建立简便快捷的水产品中多农药残留分析方法, 对于及时和准确地摸排水产品中的农药污染状况, 提早发现可能存在的安全隐患, 减少食品安全事故的出现具有重要意义。     

Leaching of metribuzin metabolites and the associated contamination of a sandy Danish aquifer

As degradation products of metribuzin have received little attention as potential groundwater contaminants, we evaluated leaching of metribuzin and its primary metabolites desaminometribuzin (DA), desaminodiketometribuzin (DADK), and diketometribuzin (DK) at a sandy test site in Denmark. Soil water and groundwater were sampled monthly over a four-year period. Leaching of metribuzin and DA was negligible. DK and DADK leached from the root zone (1 meter below ground surface (mbgs)) in average concentrations considerably exceeding the EU limit value for drinking water (0.1 microg/L). Both metabolites appear to be relatively stable and persisted in soil water and groundwater several years after application. Past application of metribuzin at the site had contaminated the groundwater with both DK and DADK, which were detected in 99% and 48%, respectively, of the groundwater samples analyzed. Except for three of the groundwater samples, the DADK concentration never exceeded the EU limit value. In contrast, the annual concentration of DK exceeded 0.1 microg/L at 90% of the screens analyzed. The present findings suggest that as the degradation products of metribuzin can leach through sandy soil in high concentrations, they could potentially contaminate the groundwater. In view of this risk DK and DADK should both be included in monitoring programs and their ecotoxicological effects should be further investigated.     

Predicting bioavailability and accumulation of organochlorine pesticides by Japanese medaka in the presence of humic acid and natural organic matter using passive sampling membranes

Adsorption to dissolved organic matter (DOM) may significantly decrease the freely dissolved concentration of many hydrophobic organic compounds and, hence, result in reduced bioavailability to aquatic organisms. Here, the suitability of using triolein-embedded cellulose acetate membrane (TECAM) as a biomimetic surrogate to assess the bioavailability of organochlorine pesticides (OCPs) in water in the presence of DOM was explored. The accumulation of OCPs was measured in TECAM and pelagic Japanese medaka (Oryzias latipes) in the laboratory after 12 h exposure to water containing different levels of Aldrich humic acid. Further, OCP uptake by TECAM and medaka in real aqueous environments was evaluated after 30 d exposures in two sites. Laboratory results showed that OCP uptake by medaka consistently decreased with increasing levels of humic acid in the range of 0-15 mg C/L in sample solutions. This tendency was closely mimicked by OCP accumulation in TECAM under the same conditions. Field results showed that TECAM accumulated similar OCP patterns as medaka (r2 = 0.92 for site 1 and r2 = 0.94 for site 2), although comparison of the in-field eight OCP concentrations in TECAM to those in medaka yielded approximately a factor of 3 (on a wet weight basis). These results suggest that the TECAM method can be used as a simple and useful tool to predict the bioavailability and bioaccumulation potential of poorly biotransformed organic compounds in pelagic fish in aqueous environment.     

Redox chemistry in Minnesota streams during episodes of increased methylmercury discharge

Mercury (Hg) and methylmercury (MeHg) are flushed from watersheds during hydrological events, contaminating downstream surface waters and resident fish populations. We monitored total mercury (THg), MeHg, and ancillary water chemistry parameters in two streams (Cedar Creek and Trott Brook) in east-central Minnesota on a weekly or semiweekly basis from April through October 2003. Heavy precipitation in late June resulted in discrete episodes of high concentrations (>1.2 ng/L) of MeHg in both streams in early July. The MeHg/THg ratio increased from 0.15 to 0.36 in Cedar Creek and from 0.13 to 0.46 in Trott Brook during the event. The high MeHg concentrations were accompanied by low dissolved oxygen concentrations and increased concentrations of dissolved organic carbon, Mn, Fe, and orthophosphate. A prolonged absence of precipitation during August and early September brought stream levels back to baseflow values, and MeHg concentrations decreased to less than 0.1 ng/L. These results suggest that warm-weather, high-discharge events are the primary route of export of MeHg from these watersheds, and baseflow contributes much less MeHg to downstream waters. The redox water chemistry during the,events sampled here suggests that MeHg in these streams is discharged from wetland areas where anoxic/anaerobic conditions prevail.     

Carbon nanotube-based electrochemical sensor for assay of salivary cholinesterase enzyme activity: an exposure biomarker of organophosphate pesticides and nerve agents

Certain saliva enzymes may be useful biomarkers for detecting exposures to organophosphate pesticides and chemical nerve agents. In this regard, saliva biomonitoring offers a simple and noninvasive approach for rapidly evaluating those exposures in real time. An electrochemical sensor coupled with a microflow injection system was developed for a simple, rapid, and sensitive characterization of cholinesterase (ChE) enzyme activities in rat saliva. The electrochemical sensor is based on a carbon nanotube (CNT)-modified screen-printed carbon electrode (SPE), which is integrated into a flow cell. Because of the excellent electrocatalytic activity of the CNTs, the sensor can detect electroactive species that are produced from enzymatic reactions with extremely high sensitivity and at low potentials. The electrochemical properties of acetylcholinesterase (AChE) enzymatic products were studied using a CNT-modified SPE, and the operation parameters such as the applied potential and substrate concentration were optimized to achieve the best performance. The AChE enzyme activity was further investigated using the CNT-based electrochemical sensor with commercially available purified AChE and ChE in saliva obtained from nave rats. It is found that the calibration curve is linear over a wide range of AChE concentrations from 5 pM to 0.5 nM, and the sensor is very sensitive with the detection limit down to 2 pM. The dynamics of the ChE enzyme activity in saliva with organophosphate pesticides was further studied using this sensor. The results showthatthe senor can be used to characterize salivary enzyme activity and to detect the exposure to organophosphate compounds. This new CNT-based electrochemical sensor thus provides a sensitive and quantitative tool for noninvasive biomonitoring of the exposure to organophosphate pesticides and nerve agents.     

A terrestrial food-chain bioaccumulation model for POPs

Mechanistic bioaccumulation models for fish and piscivorous food-webs are widely used to assess the environmental hazard and risk of commercial chemicals, develop water quality criteria and remediation objectives, and conduct exposure assessment of pesticides in aquatic systems. Similar models for mammals and terrestrial food-webs are largely absent. As a result, the hazards and risks of bioaccumulative substances in mammals, birds, and humans remain unrecognized by regulators, and current globally used criteria for identifying bioaccumulative substances only apply to water-breathing organisms and are inadequate for protecting air-breathing organisms including mammals, birds, and human beings. In this paper, we develop and test a modeling framework that can be used to estimate the biomagnification potential and the organism-soil bioaccumulation factor of organic commercial chemicals in terrestrial food-chains. We test the model for the soil-earthworm-shrew food-chain and apply the model to illustrate that (i) chemicals with an octanol-air partition coefficient (K(OA)) < 10(5.25) do not biomagnify even if the K(ow) is high and optimal for biomagnification in fish; (ii) chemicals with a K(OA) > or = 105.25 and a K(ow) between 10(1.75) and 10(12) have a biomagnification potential unless they are metabolized at a sufficiently rapid rate (e.g., in excess of 0.3 d(-1) or a half-life time of 2.5 d for shrews).