Turbid Waters and Clearer Standards: Refining Water Quality Criteria for Coastal Environments by Encompassing Metal Bioavailability from Suspended Particles.

Suspended particulate matter (SPM) carries a major fraction of metals in turbid coastal waters, markedly influencing metal bioaccumulation and posing risks to marine life. However, its effects are often overlooked in current water quality criteria for metals, primarily due to challenges in quantifying SPM's contribution. This contribution depends on the SPM concentration, metal distribution coefficients (Kd), and the bioavailability of SPM-bound metals (assimilation efficiency, AE), which can collectively be integrated as a modifying factor (MF). Accordingly, we developed a new stable isotope method to measure metal AE by individual organisms from SPM, employing the widely distributed filter-feeding clam Ruditapes philippinarum as a representative species. Assessing SPM from 23 coastal sites in China, we found average AEs of 42% for Zn, 26% for Cd, 20% for Cu, 8% for Ni, and 6% for Pb. Moreover, using stable isotope methods, we determined metal Kd of SPM from these sites, which can be well predicted by the total organic carbon and iron content (R2 = 0.977). We calculated MFs using a Monte Carlo method. The calculated MFs are in the range 9.9-43 for Pb, 8.5-37 for Zn, 2.9-9.7 for Cu, 1.4-2.7 for Ni, and 1.1-1.6 for Cd, suggesting that dissolved-metal-based criteria values should be divided by MFs to provide adequate protection to aquatic life. This study provides foundational guidelines to refine water quality criteria in turbid waters and protect coastal ecosystems.

Enhancing Sediment Bioaccumulation Predictions: Isotopically Modified Bioassay and Biodynamic Modeling for Nickel Assessment.

Quantifying metal bioaccumulation in a sedimentary environment is a valuable line of evidence when evaluating the ecological risks associated with metal-contaminated sediments. However, the precision of bioaccumulation predictions has been hindered by the challenges in accurately modeling metal influx processes. This study focuses on nickel bioaccumulation from sediment and introduces an innovative approach using the isotopically modified bioassay to directly measure nickel assimilation rates in sediment. Tested in sediments spiked with two distinct nickel concentrations, the measured Ni assimilation rates ranged from 35 to 78 ng g-1 h-1 in the Low-Ni treatment and from 96 to 320 ng g-1 h-1 in the High-Ni treatment. Integrating these rates into a biodynamic model yielded predictions of nickel bioaccumulation closely matching the measured results, demonstrating high accuracy with predictions within a factor of 3 for the Low-Ni treatment and within a factor of 1 for the High-Ni treatment. By eliminating the need to model metal uptake from various sources, this streamlined approach provides a reliable method for predicting nickel bioaccumulation in contaminated sediments. This advancement holds promise for linking bioaccumulation with metal toxicity risks in sedimentary environments, enhancing our understanding of metal-contaminated sediment risks and providing valuable insights to support informed decision-making in ecological risk assessment and management.

Improving toxicity prediction of metal-contaminated sediments by incorporating sediment properties.

For the purpose of sediment quality assessment, the prediction of toxicity risk-levels for aquatic organisms based on simple environmental measurements is desirable. One commonly used approach is the comparison of total contaminant concentrations with corresponding water and sediment quality guideline values, serving as a Line of Evidence (LoE) based on chemistry-toxicity effects relationships. However, the accuracy of toxicity predictions can be improved by considering the factors that modify contaminant bioavailability. In this study we used paired chemistry-ecotoxicity data sets for sediments to evaluate the improvement in toxicity risk predictions using bioavailability-modified guidelines. The sediments were predominantly contaminated with metals, and measurements of sediment particle size, total organic carbon (TOC) and acid volatile sulfide (AVS) were used to modify hazard quotients (HQ). To further assess the predictive efficacy of the bioavailability-modified guideline models, sediments with differing contamination levels were tested for toxicity to a benthic amphipod's reproduction. To account for differences between laboratory exposure and field exposure scenarios, where the latter creates greater dilution, both static-renewal and flow-through test procedures were employed, and flow-through resulted in lower dissolved metal concentrations in the overlying waters. We also investigated how lower AVS concentration by oxidation modified the toxicity. This study reaffirmed that consideration of factors that influence contaminant bioavailability improves toxicity risk predictions, however the improvements may be modest. The sediment particle size data had the greatest influence on the modified HQ, indicating that higher percentage of fine particle size (<63 µm) contributed most to a lower predicted toxicity. The comparison of the static-renewal and flow-through test results continue to raise important questions about the relevance of static or static-renewal toxicity test results for risk assessment decisions, as both these test designs may cause unrealistically high contributions of dissolved metals in overlying waters to toxicity. Overall, this study underscores the value of incorporating outcomes from simple and routine sediment analysis (e.g., particle size, TOC, and consideration of AVS) to enhance the predictive efficacy of toxicity risk assessments in the context of sediment quality risk assessment.

Interspecies calibration for biomonitoring metal contamination in coastal waters using oysters and mussels.

Differences in metal bioaccumulation among species make it difficult to compare biomonitoring results obtained using different marine bivalve species. To address this challenge and improve the interpretation of biomonitoring data, we studied the toxicokinetic mechanisms underlying these differences and developed a method to estimate seawater metal concentrations based on metal concentrations in the organisms. We transplanted six common species of oysters and mussels found in Chinese coastal waters into the Jiulong River estuary and monitored metal concentrations in the organisms, water, and suspended particles every three days over a six-week period. A one-compartment first-order toxicokinetic model was used to describe the relationship between metal bioaccumulation and metal concentrations in the environment. The model parameters, including aqueous uptake (ku) and dietary assimilation (kp) rate constants, and elimination rate constant (ke), were estimated using a Markov Chain Monte Carlo fitting method with a priori information from a systematic review we conducted. The toxicokinetic model successfully fitted the temporal changes in metal bioaccumulation in all six bivalve species and explained the interspecies differences. Using the calibrated models, we were able to calculate metal concentrations in the seawater at the bivalve collection sites and enable comparisons of biomonitoring data across multiple species. In conclusion, we have established a toxicokinetic framework to explain interspecies differences in metal bioaccumulation in six commonly found bivalves and provided a useful tool for interpreting biomonitoring data in coastal environments.

Higher Risks of Copper Toxicity in Turbid Waters: Quantifying the Bioavailability of Particle-Bound Metals to Set Site-Specific Water Quality Criteria.

In coastal waters, particulate metals constitute a substantial fraction of the total metals; however, the prevalent water quality criteria are primarily based on dissolved metals, seemingly neglecting the contribution of particulate metals. Here we developed a method to quantify the toxicity risk of particulate metals, and proposed a way to calculate modifying factors (MFs) for setting site-specific criteria in turbid waters. Specifically, we used a side-by-side experimental design to study copper (Cu) bioaccumulation and toxicity in an estuarine clam, Potamocorbula laevis, under the exposure to "dissolved only" and "dissolved + particulate" 65Cu. A toxicokinetic-toxicodynamic model (TK-TD) was used to quantify the processes of Cu uptake, ingestion, assimilation, egestion, and elimination, and to relate mortality risk to tissue Cu. We find that particulate Cu contributes 40-67% of the Cu bioaccumulation when the suspended particulate matter (SPM) ranges from 12 to 229 mg L-1. The Cu-bearing SPM also increases the sensitivity of organisms to internalized Cu by decreasing the internal threshold concentration (CIT) from 141 to 76.8 µg g-1. MFs were derived based on the TK-TD model to consider the contribution of particulate Cu (in the studied SPM range) for increasing Cu bioaccumulation (MF = 1.3-2.2) and toxicity (MF = 2.3-3.9). Water quality criteria derived from dissolved metal exposure need to be lowered by dividing by an MF to provide adequate protection. Overall, the method we developed provides a scientifically sound framework to manage the risks of metals in turbid waters.

Isotopically Modified Bioassay Bridges the Bioavailability and Toxicity Risk Assessment of Metals in Bedded Sediments.

The application of bioavailability-based risk assessment for the management of contaminated sediments requires new techniques to rapidly and accurately determine metal bioavailability. Here, we designed a multimetal isotopically modified bioassay to directly measure the bioavailability of different metals by tracing the change in their isotopic composition within organisms following sediment exposure. With a 24 h sediment exposure, the bioassay sensed significant bioavailability of nickel and lead within the sediment and determined that cadmium and copper exhibited low bioavailable concentrations and risk profiles. We further tested whether the metal bioavailability sensed by this new bioassay would predict the toxicity risk of metals by examining the relationship between metal bioavailability and metal toxicity to chironomid larvae emergence. A strong dose-toxicity relationship between nickel bioavailability (nickel assimilation rate) and toxicity (22 days emergence ratio) indicated exposure to bioavailable nickel in the sediment induced toxic effects to the chironomids. Overall, our study demonstrated that the isotopically modified bioassay successfully determined metal bioavailability in sediments within a relatively short period of exposure. Because of its speed of measurement, it may be used at the initial screening stage to rapidly diagnose the bioavailable contamination status of a site.

Application of a Multi-Metal Stable-Isotope-Enriched Bioassay to Assess Changes to Metal Bioavailability in Suspended Sediments.

The direct measurement of particulate contaminant bioavailability is a challenging aspect for the environmental risk assessment of contaminated sites. Here, we demonstrated a multi-metal stable-isotope-enriched bioassay to simultaneously measure the bioavailability of Cd, Cu, and Zn in naturally contaminated sediments following differing periods of resuspension treatment. Freshwater filter-feeding clams were pre-labeled with the isotopes 114Cd, 65Cu, and 68Zn to elevate isotope abundances in their tissues and then exposed to metal-contaminated suspended sediments. The assimilation of sediment-associated metals by clams would decrease the isotope ratios (Cd114/111, Cu65/63, and Zn68/64) in tissues, providing a direct measurement of metal bioavailability. For the sediments tested here, the method revealed bioavailable cadmium and non-bioavailable copper in sediments but was inconclusive for zinc. With a longer resuspension time, the bioavailability of particulate cadmium increased, but that of copper was unaffected. Metal bioavailability predicted using traditional wet-chemical extraction methods was inconsistent with these findings. The study indicated that multi-metal stable-isotope-enriched bioassay provides a new tool for directly assessing metal bioavailability in sediments, and this method is amenable for use in in situ assessments.

Field to laboratory comparison of metal accumulation on aged microplastics in coastal waters.

The ubiquity of microplastics in the environment has attracted much attention on their risks. Though newly produced plastics were considered inert to aqueous metals, a few studies suggest aged microplastics can accumulate metals. Still, knowledge gap exists on the comparability of metal accumulation in field condition and that acquired in controlled laboratory settings. Accordingly, we comparatively assessed the field accumulation and laboratory adsorption of metals on aged microplastics in coastal waters. Microplastics of different polymeric types were aged for 8 weeks at three coastal sites with different contamination levels. Microplastics accumulated metals to substantial concentrations during ageing (median concentrations, µg g-1: Fe = 950, Mn = 94, Zn = 19, Cu = 2.8, Ni = 1.7, Pb = 1.6, and Cd = 0.005). Adsorption capacity of (aged) microplastics was evaluated in laboratory using a stable isotope tracer method. At environmentally realistic concentrations (µg L-1, 114Cd = 1.7, 65Cu = 4.4, 62Ni = 5.4, 206Pb = 0.5, and 68Zn = 13), the median concentrations of newly adsorbed isotopes on the aged microplastics were 0.01, 1.4, 0.07, 0.56, and 1.1 µg g-1, respectively, one to two orders of magnitude higher than those adsorbed on pristine microplastics. However, the composition pattern of metals accumulated on aged microplastics differed from the composition of metals newly adsorbed in laboratory: the prior one reflected the contamination status of ageing sites and varied by polymeric types; whereas the laboratory newly adsorbed metals on aged microplastics were uniformly correlated to particulate Fe and Mn concentrations, suggesting Fe and Mn mineral coatings mediated the ensuing metal adsorption. Such discrepancy unveiled the complexity of metal accumulation behavior in the real environment and highlighted that cares should be taken when translating laboratory findings to risk assessment of metal contaminated microplastics in the real environment.

Measuring Metal Uptake and Loss in Individual Organisms: A Novel Double Stable Isotope Method and its Application in Explaining Body Size Effects on Cadmium Concentration in Mussels.

Interindividual variabilities in metal bioaccumulation confound our interpretation of the biomonitoring data. Measuring metal toxicokinetics in organism "individuals" may provide insights into the processes underlying the variabilities. Therefore, we developed a double stable isotope method that can simultaneously measure uptake and elimination of metals in individual organisms and thus the distribution of the toxicokinetic parameters. Specifically, we exposed organisms to both isotopes (113Cd and 114Cd; Cd = cadmium) during the first stage and to only one isotope (114Cd) during the second stage. Metal uptake and elimination rate constants (i.e., ku and ke) were simultaneously estimated from the content of the two isotopes measured in each organism at the end of the second stage. We applied the method to investigate the interindividual variability in Cd concentrations caused by body size in two marine mussel species. Cd concentrations are higher in larger Xenostrobus atratus but lower in smaller Perna viridis. Size-dependent Cd uptake is found to be responsible for size effects on Cd concentrations in the mussels and the interspecies differences in the relationship between Cd concentration and body size. Specifically, Cd ku increases with size in X. atratus (0.057-0.297 L g-1 d-1) but decreases with size in P. viridis (0.155-0.351 L g-1 d-1). In contrast, Cd ke is not influenced by body size (X. atratus: 0.002-0.060 d-1; P. viridis: 0.008-0.060 d-1). Overall, we extended the applicability of the stable isotope methods to measure metal toxicokinetics in "individual" organisms, providing a readily available tool for investigating problems related to metal bioaccumulation.

In Situ DGT Sensing of Bioavailable Metal Fluxes to Improve Toxicity Predictions for Sediments.

An increased risk of adverse biological effects of metals in sediments may be accompanied by high labile metal fluxes as measured by the diffusive gradients in thin films (DGT) technique. To improve the usefulness of the DGT technique for sediment quality risk assessments, we used the simpler and more cost-effective piston DGTs rather than planar DGT probes to measure bioavailable metal fluxes in naturally contaminated sediments with widely varying composition (properties, metals and concentrations) and assessed their prediction of toxicity to amphipod reproduction in a flow-through microcosm. DGT pistons were deployed in sediments under different conditions, both in the field (in situ) and in the laboratory in sediment cores (lab-equilibrated) and in homogenized sediments (lab-homogenized). We demonstrated that the metal flux toxic units, DGTTU, measured in situ best predicted the magnitude of toxicity to amphipod reproduction. For sediments that had been highly disturbed before testing, DGTTU were less predictive for observed toxicity, but the copper flux alone (DGTTU-Cu) was effective, indicating copper was the primary cause of toxicity in these highly perturbed sediments. Overall, our study highlighted that the adverse effects induced by excessive bioavailable metals in contaminated sediments can be consistently sensed by the DGT pistons.

Making the Biotic Ligand Model kinetic, easier to develop, and more flexible for deriving water quality criteria.

In aquatic environments, the ecological risks posed by metals are greatly affected by water chemistry, thereby creating challenges for water quality management. Biotic ligand models (BLMs) have become the most widely used tools to interpret and predict water chemistry effects. Traditional BLM development methods require a large number of toxicity tests and organisms, and model predictions are limited to certain toxicity statistics (e.g., 48-h median effective concentration, 48-h EC50), to which the models were calibrated. To address these limitations, we propose a new method to develop BLMs by integrating them into the toxicokinetic-toxicodynamic (TK-TD) framework. Metal bioaccumulation was predicted from metal exposure and water chemistry using the BLM-type toxicokinetics, whilst metal toxicity was predicted from metal bioaccumulation using the toxicodynamics. Using the new method, we developed a kinetic BLM of cadmium for Daphnia magna with only six toxicity tests and 1540 daphnids; this represents a 60-80% reduction compared to the traditional methods. The model was validated in the presence of commercial dissolved organic matter (DOM) and in natural waters sampled from 12 lakes. The kinetic BLM was able to accurately simulate the protective effects of the commercial DOM by employing the Stockholm humic model, whilst the complexation capabilities of some natural DOM were overestimated. We further used the model to predict Cd EC50 and no-effect concentrations for different waters, generating predictions close to the effect concentrations reported in the literature. Overall, our method requires fewer resources and presents an easier approach to develop BLMs; the kinetic BLM is more flexible and can serve as a useful tool for developing water quality criteria.

Contrasting temporal dynamics of dissolved and colloidal trace metals in the Pearl River Estuary.

Metal contamination in the Pearl River Estuary (PRE) is persistent-, yet a comprehensive understanding of distribution and behavior of metals in surface water of this large, multi-source estuary is still lacking. In the present study, water samples from 24 sites spanning the whole estuary during the dry and wet season were collected and fractioned. Trace metal concentrations in samples were then determined following a preconcentration technique using Nobias Chelate-PA1 resin. Distribution of trace metals exhibited variability along and across estuary, as a result of estuarine mixing, external metal loadings, addition and removal. Behavior of metals was contrasting between the dry and wet seasons, exhibiting metal-specific intercorrelations and dynamics. Colloidal metals (Mn, Ni and Cd) were primarily present in upper estuary and areas affected by external contaminant loading. Colloidal Cu was the only metal that was ubiquitous in the estuary in both seasons. It showed a high affinity for small-size organic colloids (likely fulvic acid) during the dry season. Overall, the present study demonstrated the multi-source character of the PRE and that the behavior of trace metals was controlled by the coupling of hydrologic and geochemical processes, with anthropogenic perturbations.

Using Zn Isotopic Signatures for Source Identification in a Contaminated Estuary of Southern China.

Zinc isotope ratios in water and suspended particles (SP) were measured in the Pearl River Estuary (PRE), China. Site-to-site δ66Zn values in water varied by approximately 1.3‰ (i.e., -0.66‰ to 0.65‰ relative to IRMM-3702 in August 2017). There were larger variations in δ66Zn values in water collected from the east shore (i.e., -0.66‰ to 0.37‰) of the PRE close to industrialized areas, in comparison to those from the western shore (i.e., -0.23‰ to 0.13‰), indicating that the PRE was influenced by different Zn sources. The variations in δ66Zn values in water from estuarine locations were much larger than those collected from river mouths. Similarly, larger variations in δ66Zn values were observed in suspended particles (i.e., -1.45‰ to 0.63‰) relative to the water. Zinc isotopic differences (i.e., Δ66Zn‰) between particles and water were significantly (p < 0.05) and linearly correlated with Zn concentrations in particles between 0.8 and 10 µm in size at most of the estuary stations, suggesting that Zn partitioning between dissolved and particulate phases influences the observed differences in Zn isotope ratios. A significant (p < 0.0001) linear correlation between the predicted δ66Zn values (using variations in water salinities) vs observed δ66Zn values indicates that Zn isotope ratios in water in the PRE can be useful for predicting the mixing processes in the water.

Bioturbation effects on metal release from contaminated sediments are metal-dependent.

Metal flux measurements inform the mobility, potential bioavailability and risk of toxicity for metals in contaminated sediments and therefore is an important approach for sediment quality assessment. The binding and release of metals that contribute to the net flux is strongly influenced by the presence and behaviors of benthic organisms. Here we studied the effects of bioturbation on the mobility and efflux of metals from multi-metal contaminated sediments that inhabited by oligochaete worms or both worms and bivalves. Presence of bivalves enhanced the release of Mn, Co, Ni and Zn but not for copper and chromium, which is likely due to the high affinities of copper and chromium for the solid phase. Metals in the overlying water were primarily associated with fractions smaller than 10 kDa, and the fractionation of all metals were not affected by the presence of the bivalve. Metal fluxes attributed to different processes were also distinguished, and the bioturbation induced effluxes were substantially higher than the diffusive effluxes. Temporal variabilities in the total net effluxes of Mn, Co, Ni and Zn were also observed and were attributed to the biological activities of the bivalves. Overall, the present study demonstrated that the response of different metals to the same bioturbation behavior was different, resulting in distinct mobility and fate of the metal contaminants.

Impact of phenol on the performance, kinetics, microbial communities and functional genes of an autotrophic denitrification system.

Nitrate and phenol often co-occur in wastewater because of the complex industrial and agricultural processes, while the impacts of phenol on autotrophic denitrification remain unclear. Here, a sulfur and hydrogen-oxidizing autotrophic denitrification reactor was established, and the effects of different concentrations of phenol on the nitrate removal performance, kinetics, microbial communities, and functional genes were investigated. Increasing concentrations of phenol significantly decreased the denitrification efficiency in the reactor. The kinetic data indicate the limitation of nitrate diffusion may be one of reasons. Increasing phenol concentrations declined the activities of nitrate and nitrite reductases and induced the production of reactive oxygen species (ROS) and the release of lactate dehydrogenase (LDH), suggesting potential toxicity to the denitrifying consortium. Denitrifying gene nirK was most sensitive to phenol stresses in the reactor. In addition, Thauera was the predominant genus in system with and without phenol, Bacillus was enriched under high phenol concentrations.

Effects of resuspension on the mobility and chemical speciation of zinc in contaminated sediments.

Identifying and quantifying the processes governing the mobilization of metals during resuspension events is key to assessing long-term metals efflux from sediments and associated ecological impacts. We investigated the effects of sediment resuspension on the mobilization and chemical speciation of zinc in two-week-long batch experiments using metal-contaminated sediments from Lake DePue (IL, USA). Measurements of dissolved zinc and sulfate allowed us to characterize the kinetics of metal sulfide dissolution and the resulting net release of zinc to the aqueous phase. X-ray absorption spectroscopy (XAS) provided direct insights into the chemical speciation of iron and zinc and their dynamic transformations during resuspension. While ZnS rapidly oxidized during resuspension, dissolved zinc increased only after two days of resuspension. We proposed a kinetic model to explain changes in the chemical speciation of zinc during these experiments as constrained by the dissolved species concentrations and chemical speciation as informed by XAS. Only 15% of the zinc mobilized was released to the aqueous phase while the remaining fraction repartitioned the solid phase either as a carbonate precipitate or as a sorbed species. Our results show that zinc sorption onto particle surfaces and reprecipitation of zinc minerals limit zinc solubility during resuspension of metal-sulfide sediments.

Spatial and temporal variations of bulk and colloidal dissolved organic matter in a large anthropogenically perturbed estuary.

In the present study, we characterized the sources of dissolved organic matter (DOM) and the processes controlling the evolution of DOM in a large anthropogenically perturbed estuary in Southern China. Three-dimensional excitation emission matrices (3D EEMs) revealed that DOM in the estuary was primarily from autochthonous origin although terrestrial sources also contributed to the DOM production. Parallel factor analysis (PARAFAC) of the EEMs dataset indicated that DOM in the estuary was a legacy from the upstream wastewater discharging activities, and estuarine mixing was the primary mechanism responsible for the decreasing concentrations of DOM components. However, non-conservative behavior of DOM components was also observed along the center transect as a result of additional removal process and spatial heterogeneity in the distribution of DOM. Seasonal influence on the concentrations and compositions of colloidal DOM in the estuary was also found. Asymmetric flow field-flow fractionation (AF4) analysis showed distinct distribution patterns of the colloidal DOM during the dry and wet seasons. Behavior of colloidal DOM was size-independent and the distribution of colloidal DOM was controlled by multiple depletion and replenishment cycles in the dry season, in contrast to those observed in the wet season. By combining both EEMs-PARAFAC modeling and AF4 technique, this study provided important information on the sources and fate of bulk and colloidal DOM in a large estuary with intensive anthropogenic influences.

Interplay between flow and bioturbation enhances metal efflux from low-permeability sediments.

Understanding the interplay effects between processes such as hydrodynamic forcing, sediment resuspension, and bioturbation is key to assessment of contaminated sediments. In the current study, effects of hydrodynamic forcing, sediment resuspension, and bioturbation by the marine polychaete Nereis virens were evaluated both independently and together in a six-month flume experiment. The results show that hydrodynamic forcing without resuspension or worm action slightly enhanced efflux of dissolved Cu to the water column, sediment resuspension released considerable amounts of dissolved Cu, and interactions between hydrodynamics and worm burrowing further enhanced Cu efflux. In non-bioturbated sediments, fine particles were only resuspended to the overlying water under the highest imposed shear stress, 0.58Pa. However, bioturbated sediments were resuspended under all shear stresses tested (0.11-0.58Pa), indicating that bioturbation destabilized the sediment bed. Further, increases in fluid shear following bioturbation caused rapid releases of dissolved Cu to the overlying water within a few hours. Cu efflux under fluid shears of 0.47Pa and 0.58Pa were 360× and 15× greater after the introduction of worms compared with the same flow conditions without their presence. Overall, our results indicate that the release of metals from low-permeability sediments is greatly enhanced by interactions between flow and bioturbation.

An Integrated Experimental and Modeling Approach to Predict Sediment Mixing from Benthic Burrowing Behavior.

Bioturbation is the dominant mode of sediment transport in many aquatic environments and strongly influences both sediment biogeochemistry and contaminant fate. Available bioturbation models rely on highly simplified biodiffusion formulations that inadequately capture the behavior of many benthic organisms. We present a novel experimental and modeling approach that uses time-lapse imagery to directly relate burrow formation to resulting sediment mixing. We paired white-light imaging of burrow formation with fluorescence imaging of tracer particle redistribution by the oligochaete Lumbriculus variegatus. We used the observed burrow formation statistics and organism density to parametrize a parsimonious model for sediment mixing based on fundamental random walk theory. Worms burrowed over a range of times and depths, resulting in homogenization of sediments near the sediment-water interface, rapid nonlocal transport of tracer particles to deep sediments, and large areas of unperturbed sediments. Our fundamental, parsimonious random walk model captures the central features of this highly heterogeneous sediment bioturbation, including evolution of the sediment-water interface coupled with rapid near-surface mixing and anomalous late-time mixing resulting from infrequent, deep burrowing events. This approach provides a general, transferable framework for explicitly linking sediment transport to governing biophysical processes.

Lifetime and dissolution kinetics of zinc oxide nanoparticles in aqueous media.

We have assessed the persistence and lifetime of ZnO nanoparticles (ZnO-NPs) by performing dissolution experiments in three different aqueous media. These experiments were performed at ZnO-NP concentration levels close to the solubility of zincite (∼8 µM or 650 µg l(-1) of ZnO)-a concentration that is orders of magnitude higher than current estimated relevant environmental concentrations. The kinetics were followed by voltammetry, while maintaining the pH at about 7.5 using a CO2/N2 gas mixture to remove di-oxygen interference. Our results show that, under these conditions, ZnO-NPs readily dissolve with a lifetime expectancy that does not exceed 90 min. Water chemistry, especially the presence of dissolved organic matter (DOM), plays an important role in ZnO-NP dissolution. Dissolution rates significantly increase in the presence of strong chelating agents, EDTA and L-cysteine, while the addition of polymeric DOM, such as sodium alginate, has the opposite effect. Our results suggest that ZnO-NPs are unlikely to persist in natural aqueous media and that the toxicity should be primarily related to the released Zn(2+) ions rather than effects commonly associated to the presence of nanoparticles.