Evidence of a rapid phosphorus-induced regime shift in a large deep reservoir.

Ecological regime shift studies in freshwater systems are mainly limited to shallow lakes and reservoirs, while abrupt changes in deeper lakes are often attributed to climate change. Here, we demonstrate the application of regime shift theory to one of California's newest and deepest reservoirs, Diamond Valley Lake (DVL), which in recent years showed an unexpected rapid departure from its water quality conditions of the previous decade. The reservoir shifted from a well oxygenated condition with low phytoplankton growth to a hypoxic, phytoplankton-dominated turbid system. We statistically identified the critical stressor (phosphorus (P)), switch points, and its load threshold and characterized its transition to an alternative stable state and the stabilizing mechanisms contributing to hysteresis. We analyzed long-term environmental, chemical and flow data, conducted a hydrographic survey, and developed a hydrodynamic model to characterize the factors that contributed to regime shift and to evaluate different management strategies that might reverse this shift. Our findings indicate that large deep systems exhibit different transition dynamics in the presence of an acute stressor compared to regime shifts in shallow systems. A cumulative external TP load threshold of 4.6 mg m-2 d-1 added to the reservoir over nearly 11 months was identified as the critical stressor. For large deep systems, inherent morphometric features such as large relative depth combine with external stressors to drive regime shifts. Light winds, morphometric conditions impeding deep mixing, and a stable stratification that lasts up to 9 months makes DVL more susceptible to hypolimnetic hypoxia, an intrinsic factor accelerating regime shift. Results also suggest regime shift occurred in 2013, when new limnological processes were established to reinforce the new alternative stable state and existing ecosystem services were impaired. Interactions between hypoxia, internal P loading (~2.1 mg m-2 d-1), and seasonal cyanobacterial blooms were identified as mechanisms perpetuating the new alternative state.

Effects of glucose on the performance of enhanced biological phosphorus removal activated sludge enriched with acetate.

The effects of glucose on enhanced biological phosphorus removal (EBPR) activated sludge enriched with acetate was investigated using sequencing batch reactors. A glucose/acetate mixture was serially added to the test reactor in ratios of 25/75%, 50/50%, and 75/25% and the EBPR activity was compared to the control reactor fed with 100% acetate. P removal increased at a statistically significant level to a near-complete in the test reactor when the mixture increased to 50/50%. However, EBPR deteriorated when the glucose/acetate mixture increased to 75/25% in the test reactor and when the control reactor abruptly switched to 100% glucose. These results, in contrast to the EBPR conventional wisdom, suggest that the addition of glucose at moderate levels in wastewaters does not impede and may enhance EBPR, and that glucose waste products should be explored as an economical sustainable alternative when COD enhancement of EBPR is needed.

Nonsingular adsorption/desorption of chlorpyrifos in soils and sediments: experimental results and modeling.

At environmentally relevant concentrations in soils and sediments, chlorpyrifos, a hydrophobic organic insecticide, showed strong adsorption that correlated significantly with organic matter content. Chlorpyrifos desorption followed a nonsingular falling desorption isotherm that was estimated using a memory-dependent mathematical model. Desorption of chlorpyrifos was biphasic in nature, with a labile and nonlabile component. The labile component comprised 18-28% of the original solid-phase concentration, and the residue was predicted to slowly partition to the aqueous phase, implying long-term desorption from contaminated soils or sediments. The newly proposed mechanism to explain sorption/desorption hysteresis and biphasic desorption is the unfavorable thermodynamic energy landscape arising from limitation of diffusivity of water molecules through the strongly hydrophobic domain of soils and sediments. Modeling results suggest that contaminated soils and sediments could be secondary long-term sources of pollution. Long-term desorption may explain the detection of chlorpyrifos and other hydrophobic organic compounds in aquatic systems far from application sites, an observation that contradicts conventional transport predictions.

Adsorption and desorption of chlorpyrifos to soils and sediments.

Chlorpyrifos, one of the most widely used insecticides, has been detected in air, rain, marine sediments, surface waters, drinking water wells, and solid and liquid dietary samples collected from urban and rural areas. Its metabolite, TCP, has also been widely detected in urinary samples collected from people of various age groups. With a goal of elucidating the factors that control the environmental contamination, impact, persistence, and ecotoxicity of chlorpyrifos, we examine, in this review, the peer-reviewed literature relating to chlorpyrifos adsorption and desorption behavior in various solid-phase matrices. Adsorption tends to reduce chlorpyrifos mobility, but adsorption to erodible particulates, dissolved organic matter, or mobile inorganic colloids enhances its mobility. Adsorption to suspended sediments and particulates constitutes a major off-site migration route for chlorpyrifos to surface waters, wherein it poses a potential danger to aquatic organisms. Adsorption increases the persistence of chlorpyrifos in the environment by reducing its avail- ability to a wide range of dissipative and degradative forces, whereas the effect of adsorption on its ecotoxicity is dependent upon the route of exposure. Chlorpyrifos adsorbs to soils, aquatic sediments, organic matter, and clay minerals to differing degrees. Its adsorption strongly correlates with organic carbon con- tent of the soils and sediments. A comprehensive review of studies that relied on the batch equilibrium technique yields mean and median Kd values for chlorpyrifos of 271 and 116 L/kg for soils, and 385 and 403 L/kg for aquatic sediments. Chlorpyrifos adsorption coefficients spanned two orders of magnitude in soils. Normalizing the partition coefficient to organic content failed to substantially reduce variability to commonly acceptable level of variation. Mean and median values for chlorpyrifos partition coefficients normalized to organic carbon, K, were 8,163 and 7,227 L/kg for soils and 13,439 and 15,500 L/kg for sediipents. This variation may result from several factors, including various experimental artifacts, variation in quality of soil organic matter, and inconsistencies in experimental methodologies. Based on this review, there appears to be no definitive quantification of chlorpyrifos adsorption or desorption characteristics. Thus, it is difficult to predict its adsorptive behavior with certainty, without resorting to experimental methods specific to the soil or sediment of interest. This limitation should be recognized in the context of current efforts to predict the risk, fate, and transport of chlorpyrifos based upon published partition coefficients. Based on a comprehensive review of the peer-reviewed literature related to adsorption and desorption of chlorpyrifos, we propose the following key areas for future research. From this review, it becomes increasingly evident that pesticide partitioning cannot be fully accounted for by the fraction of soil or solid-matrix organic matter or carbon content. Therefore, research that probes the variation in the nature and quality of soil organic matter on pesticide adsorption is highly desirable. Pesticide persistence and bioavailability depend on insights into desorption capacity. Therefore, understanding the fate and environmental impact of hydrophobic pesticides is incomplete without new research being performed to improve insights into pesticide desorption from soils and sediments. There is also a need for greater attention and consistency in developing experimental methods aimed at estimating partition coefficients. Moreover, in such testing, choosing initial concentrations and liquid-solid ratios that are more representative of environmental conditions could improve usefulness and interpretation of data that are obtained. Future monitoring efforts should include the sampling and analysis of suspended particulates to account for suspended solid-phase CPF, a commonly underestimated fraction in surface water quality monitoring programs. Finally, management practices related to the reduction of off-site migration of CPF should be further evaluated, including alternative agricultural practices leading to reduction in soil erosion and structural best management practices, such as sedimentation ponds, treatment wetlands, and vegetated edge-of-field strips.

Research advances and challenges in the microbiology of enhanced biological phosphorus removal--a critical review.

Enhanced biological phosphorus removal (EBPR) is a well-established technology for removing phosphorus from wastewater. However, the process remains operationally unstable in many systems, primarily because there is a lack of understanding regarding the microbiology of EBPR. This paper presents a review of advances made in the study of EBPR microbiology and focuses on the identification, enrichment, classification, morphology, and metabolic capacity of polyphosphate- and glycogen-accumulating organisms. The paper also highlights knowledge gaps and research challenges in the field of EBPR microbiology. Based on the review, the following recommendations regarding the future direction of EBPR microbial research were developed: (1) shifting from a reductionist approach to a more holistic system-based approach, (2) using a combination of culture-dependent and culture-independent techniques in characterizing microbial composition, (3) integrating ecological principles into system design to enhance stability, and (4) reexamining current theoretical explanations of why and how EBPR occurs.

Effects of drain-fill cycling on chlorpyrifos mineralization in wetland sediment-water microcosms.

Constructed treatment wetlands are efficient at retaining a range of pesticides, however the ultimate fate of many of these compound is not well understood. This study evaluated the effect of drain-fill cycling on the mineralization of chlorpyrifos, a commonly used organophosphate insecticide, in wetland sediment-water microcosms. Monitoring of the fate of (14)C ring-labeled chlorpyrifos showed that drain-fill cycling resulted in significantly lower mineralization rates relative to permanently flooded conditions. The reduction in mineralization was linked to enhanced partitioning of the pesticide to the sediment phase, which could potentially inhibit chlorpyrifos hydrolysis and mineralization. Over the nearly two-month experiment, less than 2.5% of the added compound was mineralized. While rates of mineralization in this experiment were higher than those reported for other soils and sediments, their low magnitude underscores how persistent chlorpyrifos and its metabolites are in aquatic environments, and suggests that management strategies and ecological risk assessment should focus more on ultimate mineralization rather than the simple disappearance of the parent compound.