The acid volatile sulphide (AVS) and simultaneously extracted metals (ΣSEM) method is increasingly used for risk assessment of toxic metals. In this study, we assessed spatial and temporal variations of AVS and ΣSEM in river sediments and floodplain soils, addressing influence of flow regime and flooding. Slow-flowing sites contained high organic matter and clay content, leading to anoxic conditions, and subsequent AVS formation and binding of metals. Seasonality affected these processes through temperature and oxygen concentration, leading to increased levels of AVS in summer at slow-flowing sites (max. 37 μmol g-1). In contrast, fast-flowing sites hardly contained AVS, so that seasonality had no influence on these sites. Floodplain soils showed an opposite AVS seasonality because of preferential inundation and concomitant AVS formation in winter (max. 3-30 μmol g-1). We conclude that in dynamic river systems, flow velocity is the key to understanding variability of AVS and ΣSEM. Flow velocity is the key to understanding variability of AVS and ΣSEM in river sediment.

Organophosphorus pesticides (OPs) are ubiquitous in the environment and are highly toxic to amphibians. They deactivate cholinesterase, resulting in neurological dysfunction. Most chemicals in this group require oxidative desulfuration to achieve their greatest cholinesterase-inhibiting potencies. Oxon derivatives are formed within liver cells but also by bacterial decay of parental pesticides. This study examines the toxicity of chlorpyrifos, malathion and diazinon and their oxons on the foothill yellow-legged frog (Rana boylii). R. boylii is exposed to agricultural pesticides in the California Central Valley. Median lethal concentrations of the parental forms during a 96 h exposure were 3.00 mg/L (24 h) for chlorpyrifos, 2.14 mg/L for malathion and 7.49 mg/L for diazinon. Corresponding oxons were 10 to 100 times more toxic than their parental forms. We conclude that environmental concentrations of these pesticides can be harmful to R. boylii populations. Laboratory tests on the toxicity of OP insecticides and their oxons suggest that they may be acutely lethal to amphibians at ecologically relevant concentrations.

Concern regarding the impacts of continued nitrogen and sulfur deposition on ecosystem health has prompted the development of critical acid load assessments for forest soils. A critical acid load is a quantitative estimate of exposure to one or more pollutants at or above which harmful acidification-related effects on sensitive elements of the environment occur. A pollutant load in excess of a critical acid load is termed exceedance. This study combined a simple mass balance equation with national-scale databases to estimate critical acid load and exceedance for forest soils at a 1-km2 spatial resolution across the conterminous US. This study estimated that about 15% of US forest soils are in exceedance of their critical acid load by more than 250 eq ha-1 yr-1, including much of New England and West Virginia. Very few areas of exceedance were predicted in the western US. This simple mass balance equation estimated that 17% of US forest soils exceed their critical acid load by more than 250 eq ha-1 yr-1, and these areas are predominantly located in the northeastern US.

Since the beginning of the 19th century humans have increasingly fixed atmospheric nitrogen as ammonia to be used as fertilizer. The fertilizers are necessary to create amino acids and carbohydrates in plants to feed animals and humans. The efficiency with which the fertilizers eventually reach humans is very small: 5-15%, with much of the remainder lost to the environment. The global industrial production of ammonia amounts to 117 Mton NH3-N year-1 (for 2004). By comparison, we calculate that anthropogenic emissions of NH3 to the atmosphere over the lifecycle of industrial NH3 in agriculture are 45.3 Mton NH3-N year-1, about half the industrial production. Once emitted ammonia has a central role in many environmental issues. We expect an increase in fertilizer use through increasing demands for food and biofuels as population increases. Therefore, management of ammonia or abatement is necessary. Half of industrial ammonia production is eventually lost to the global environment with significant effects.

The spatial pattern and magnitude of mass fluxes at the stream-aquifer interface have important implications for the fate and transport of contaminants in river basins. Integral pumping tests were performed to quantify average concentrations of chlorinated benzenes in an unconfined aquifer partially penetrated by a stream. Four pumping wells were operated simultaneously for a time period of 5 days and sampled for contaminant concentrations. Streambed temperatures were mapped at multiple depths along a 60 m long stream reach to identify the spatial patterns of groundwater discharge and to quantify water fluxes at the stream-aquifer interface. The combined interpretation of the results showed average potential contaminant mass fluxes from the aquifer to the stream of 272 μg m-2 d-1 MCB and 71 μg m-2 d-1 DCB, respectively. This methodology combines a large-scale assessment of aquifer contamination with a high-resolution survey of groundwater discharge zones to estimate contaminant mass fluxes between aquifer and stream. We provide a new methodology to quantify the potential contaminant mass flux from an aquifer to a stream.

To determine the source of dissolved inorganic nitrogen (N) in runoff, approx. 35 kg N enriched with the stable isotope 15N (2110[per thousand] δ15N) was added to a mature coniferous forested catchment for one whole year. The total N input was approx. 50 kg ha-1 year-1. The enrichment study was part of a long-term whole-catchment ammonium nitrate addition experiment at Gårdsjön, Sweden. The 15N concentrations in precipitation, throughfall, runoff and upper forest floor were measured prior to, during, and 3-9 years following the 15N addition. During the year of the 15N addition the δ15N level in runoff largely reflected the level in incoming N, indicating that the leached NO3- came predominantly from precipitation. Only 1.1% of the incoming N was lost during the year of the tracer addition. The cumulative loss of tracer N over a 10-year period was only 3.9% as DIN and 1.1% as DON. 15N tracer addition showed that initially the main source of NO3- in runoff was N from atmospheric deposition.

The mobilization of chromium and nickel from an industrial soil was investigated using two biodegradable chelants (citric acid and histidine), compared with a persistent one (ethylenediaminetetraacetic acid). Successive metal mobilizations were carried out in batch experiments. The main reactions involved were estimated by modeling the system with MINEQL+. For a single mobilization, citric acid was the most effective for Cr mobilization and EDTA for Ni. Their effectiveness could be explained by their ability to solubilize the mineral matrix and by the competition for the surfaces sites to desorb Cr(VI). Before and after the mobilizations, the distribution of metals was determined by a sequential extraction procedure. Only slight modifications were observed due to the low percentage of solubilized metal. A concentration of 0.05 mol L-1 (citric acid and EDTA) allows a good compromise between metal mobilization and preservation of the soil mineral integrity. Chelant-induced dissolution of soil mineral matrix controls metal solubilization.

This study examined the effects of heavy metals and plant arsenic uptake on soil arsenic distribution. Chemical fractionation of an arsenic-contaminated soil spiked with 50 or 200 mg kg-1 Ni, Zn, Cd or Pb was performed before and after growing the arsenic hyperaccumulator Pteris vittata L for 8 weeks using NH4Cl (water-soluble plus exchangeable, WE-As), NH4F (Al-As), NaOH (Fe-As), and H2SO4 (Ca-As). Arsenic in the soil was present primarily as the recalcitrant forms with Ca-As being the dominant fraction (45%). Arsenic taken up by P. vittata was from all fractions though Ca-As contributed the most (51-71% reduction). After 8 weeks of plant growth, the Al-As and Fe-As fractions were significantly (p < 0.01) greater in the metal-spiked soils than the control, with changes in the WE-As fraction being significantly (p = 0.007) correlated with plant arsenic removal. The plant's ability to solubilize soil arsenic from recalcitrant fractions may have enhanced its ability to hyperaccumulate arsenic. Arsenic taken up by P. vittata was from all fractions with most from the Ca-fraction.

The purpose of this study is to develop a mechanistic model to describe a conceptually new “flux-biological response” approach based on biotic ligand model (BLM) and Michaelis-Menten (M-M) kinetics to allow the linkage between valve closure behavior and sodium (Na) transport mechanism in freshwater clam Corbicula fluminea in response to waterborne copper (Cu). We test the proposed model against published data regarding Na uptake kinetics in rainbow trout and Na uptake profile in C. fluminea, confirming that the predictive model is robust. Here, we show that the predicted M-M maximum Cu internalization flux in C. fluminea is 0.369 μmol g-1 h-1 with a half-saturation affinity constant of 7.87 x 10-3 μM. Dynamics of Na uptake and valve closure daily rhythm driven by external Cu can also be predicted simultaneously. We suggest that this “Na transport-valve closure behavior” approach might provide the basis of a future design of biomonitoring tool. A new flux-biological response model can link valve closure and sodium transport mechanisms in freshwater clam in response to copper.

The first report on oxidant-induced plant damage in the Valley of Mexico was presented over 30 years ago. Ozone is known to occur in the Mexico City Metropolitan Area and elsewhere as the cause of chlorotic mottling on pine needles that are 2 years old or older as observed in 1976 on Pinus hartwegii and Pinus leiophylla. Visible evidences for the negative effects of ozone on the vegetation of central Mexico include foliar injury expressed as chlorotic mottling and premature defoliation on pines, a general decline of sacred fir, visible symptoms on native forest broadleaved species (e.g. Mexican black cherry). Recent investigations have also indicated that indirect effects are occurring such as limited root colonization by symbiotic fungi on ozone-damaged P. hartwegii trees and a negative influence of the pollutant on the natural regeneration of this species. The negative ozone-induced effects on the vegetation will most likely continue to increase. Ozone induced symptoms, poor tree regeneration and limited root colonization by mycorrhiza fungi observed in the valley of Mexico.