Marc W. Beutel

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.

Hypolimnetic Anoxia and Sediment Oxygen Demand in California Drinking Water Reservoirs

ABSTRACT Summertime hypolimnetic anoxia can occur in productive drinking water reservoirs as a result of the decay of phytoplankton. Anoxic conditions promote ecological processes that degrade water quality through the release of problem-causing compounds from anoxic sediments including phosphates, ammonia, sulfides, methyl-mercury, iron and manganese. Hypolimnetic aeration systems are commonly installed in reservoirs to prevent hypolimnetic anoxia, but these systems have been historically undersized due to an underestimation of the magnitude of oxygen demand in the hypolimnion. To gain insight into the sizing of hypolimnetic aeration systems, this study evaluated the effects of water current and DO concentration near the sediment-water interface on sediment oxygen demand (SOD) in nine California drinking water reservoirs of various size (5–220 million m3) and trophic status (mean annual chlorophyll a of 0.5–11 μg L−1). SOD measured under quiescent conditions in 1.8 L experimental chambers ranged from 0.1–0.8 g m2 d1 Currents near the sediment-water interface of 3–8 cm s1 induced a two to four-fold increase in SOD, and resulted in a shift from first-order to zero-order DO uptake by sediment with respect to DO concentration in overlaying water. Results support the diffusive boundary layer model for SOD, with increased DO concentration and currents resulting in a larger SOD since there is a greater diffusional driving force across a smaller diffusive boundary layer. The study also evaluated the effects of trophic status and morphometry on hypolimnetic anoxia at the nine study sites. A number of significant correlations were discovered between factor quantifying hypolimnetic anoxia (areal and mass based hypolimnetic oxygen demand, SOD) and those quantifying morphometry (mean depth of the hypolimnion, volume of the hypolimnion) and trophic status (mean annual chlorophyll a). These results suggest that both increased size of the hypolimnion and higher productivity lead to higher oxygen demand within the hypolimnion. In addition, shallower reservoirs had a larger fraction of their total oxygen demand exerted in the sediments versus the water column. As a result, increased mixing at the sediment-water interface after start-up of aeration systems, and the resulting stimulation of SOD, will be particularly important in productive reservoirs of moderate depth (mean depth of 10–15 m). Aeration systems should be designed to enhance SOD by maintaining high oxygen concentrations and by inducing currents at the sediment-water interface. This will increase the depth of penetration of DO into sediment and promote beneficial aerobic biogeochemical reactions in surface sediments. Aeration systems that utilize pure-oxygen with horizontal discharge of highly oxygenated water across the sediment surface, rather than the traditional air-lift aeration system, will be more successful in satisfying SOD and improving hypolimnetic water quality.

Effects of oxygen and nitrate on nutrient release from profundal sediments of a large, oligo-mesotrophic reservoir, Lake Mathews, California

Abstract Lake Mathews is a large, oligo-mesotrophic reservoir located in Southern California. The reservoir has elevated levels of nitrate and periodically experiences hypolimnetic anoxia. Experimental sediment-water chamber incubations and reservoir water quality monitoring were conducted to evaluate how oxygen and nitrate in overlaying water affect nutrient release from profundal sediments and internal nutrient loading. In experimental incubations, under nitrate-free anoxic conditions, sediment nutrient release rates were 3.4 ± 0.8 mg-P/m2 ·d for phosphate and 2.8 ± 1.2 mg-N/m2 ·d for ammonia (average ± standard deviation; n = 6). Oxygen repressed phosphate release and greatly diminished ammonia release from sediments in experimental incubations while nitrate only repressed phosphate release. Similar nutrient release dynamics were observed in the reservoir. Nutrient release rates estimated from seasonal nutrient profiles collected from the reservoir were 3.4 mg-P/m2 ·d for phosphate and 2.5 mg-N/m2 ·d for ammonia. Ammonia accumulation in the hypolimnion commenced with the onset of anoxic conditions, but phosphate accumulation did not start until nitrate disappeared from bottom waters approximately 6 weeks later. The time lag decreased total internal phosphorus loading by approximately 25% relative to hypothetical nitrate-free conditions. Laboratory and field data show that both oxygen and nitrate repress sediment phosphate release, likely via the maintenance of an oxidized surficial sediment layer that retains phosphate in iron-oxide complexes. However, only oxygen and not nitrate was effective in decreasing sediment ammonia release, likely by enhancing biological nitrification and assimilation in surficial sediments under oxic conditions. A number of in-lake management strategies have been developed to inhibit internal nutrient loading including calcium nitrate addition, aluminum sulfate addition, and oxygenation. In our view, the deliberate addition of nitrate to lakes and reservoirs poses several risks that must be carefully considered when evaluating strategies to control sediment phosphorus release.

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.

Effects of hypolimnetic oxygen addition on mercury bioaccumulation in Twin Lakes, Washington, USA

Twin Lakes, located on the Confederated Tribes of the Colville Indian Reservation in eastern Washington, USA, include North Twin Lake (NT) and South Twin Lake (ST). The mesotrophic, dimictic lakes are important recreational fishing sites for both warm-water bass and cold-water trout. To improve summertime cold-water habitat for trout in NT, dissolved oxygen (DO) addition to the hypolimnion, using liquid oxygen as an oxygen gas source, started in 2009. This study assessed mercury (Hg) in the water column, zooplankton and fish, and related water quality parameters, in Twin Lakes from 2009 to 2012. Because methylmercury (MeHg) buildup in lake bottom water is commonly associated with hypolimnetic anoxia, hypolimnetic oxygenation was hypothesized to reduce Hg in bottom waters and biota in NT relative to ST. Oxygen addition led to significantly higher DO (mean hypolimnetic DO: 2-8 mg/L versus <1 mg/L) and lower MeHg (peak mean hypolimnetic MeHg: 0.05-0.2 ng/L versus 0.15-0.4 ng/L) in North Twin. In North Twin, years with higher DO (2009 and 2011) exhibited lower MeHg in bottom waters and lower total Hg in zooplankton, inferring a positive linkage between oxygen addition and lower bioaccumulation. However, when comparing between the two lakes, Hg levels were significantly higher in zooplankton (total Hg range: 100-200 versus 50-100 μg/kg dry weight) and trout (spring 2010 stocking cohort of eastern brook trout mean total Hg: 74.9 versus 49.9 μg/kg wet weight) in NT relative to ST. Lower Hg bioaccumulation in ST compared to NT may be related to bloom dilution in chlorophyll-rich bottom waters, a vertical disconnect between the location of zooplankton and MeHg in the water column, and high binding affinity between sulfide and MeHg in bottom waters.

Newman Lake restoration: A case study Part III. Hypolimnetic oxygenation

Abstract Since the mid-20th century, oxygen status at the sediment–water interface (SWI) has been implicated in regulating lake internal phosphorus loading. In deeper lakes, summer hypolimnetic oxygen depletion may thus play a critical role in phosphorus cycling and lake trophic status. Hypolimnetic aeration (HA) has been utilized for more than 4 decades to prevent development of anoxia, decrease internal phosphorus load, and enhance fisheries. Most recently, interest has shifted to hypolimnetic oxygenation (HO) for potential performance and economic advantages. In Newman Lake, hypolimnetic oxygenation was initiated in 1992 when the first lake application of downflow contact bubble oxygenation (Speece Cone technology) was installed. Oxygenation at Newman has reduced growing season Nürnberg Anoxic Factors (AF) from a range of about 30–60 d to <10 d. We propose that differences in predicted versus observed AF based on phosphorus may be utilized to assess lake restoration performance. Newman Lake has demonstrated the importance of operating the system at full capacity, as lower oxygen delivery rates do not produce proportional hypolimnetic oxygen concentrations, as well as other insights into HO system sizing and design.

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.

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.

High Rates of Ammonia Removal in Experimental Oxygen-Activated Nitrification Wetland Mesocosms

While constructed treatment wetlands are very efficient at polishing nitrate from secondary effluent, they are much less effective at removing ammonia. A key factor that limits ammonia oxidation via biological nitrification in vegetated wetlands is low levels of dissolved oxygen. This study evaluated the effectiveness of side-stream oxygenation to enhance ammonia removal in replicate surface-flow experimental mesocosms containing wetland sediment and plants (Typha spp.). Mesocosms had a water volume of 29.5 L, a hydraulic retention time of 5 days, and a hydraulic loading rate of 4.3 cm/d, and were loaded with synthetic secondary effluent contain 10 mg-N/L of ammonia. Relative to nonoxygenated controls, oxygenation increased ammonia removal rates by an order of magnitude. Areal removal rates increased from 40 mg-N/ m2 /d to 450 mg-N/ m2 /d , concentration removal efficiency increased from 10 to 95%, and area-based first-order removal rates increased from <2 m/year to 50–75 m/year. Ammonia removal rates in ...

Metallogeny, exploitation and environmental impact of the Mt. Amiata mercury ore district (Southern Tuscany, Italy)

The Mt. Amiata mining district (Southern Tuscany, Italy) is a world class Hg district, with a cumulate production of more than 100,000 tonnes of Hg, mostly occurring between 1870 and 1980. The Hg mineralization at Mt. Amiata is younger than 0.3 Ma, and is directly related to shallow hydrothermal systems similar to presentday geothermal fields of the region. There is likely a continuum of Hg deposition to present day, because Hg emission from geothermal power plants is on-going. In this sense, the Mt. Amiata deposits present some analogies with hot-spring type deposits of western USA, although an ore deposit model for the district has not been established. Specifically, the source of Hg remains highly speculative. The mineralizing hydrothermal fluids are of low temperature, and of essentially meteoric origin. Recent results by our research group indicate that, 30 years after mine closure, the environmental effects of Hg contamination related to mining are still recorded by the ecosystem, namely on waterways of the Paglia and Tiber River basins. In particular, the close spatial connection between the town of Abbadia San Salvatore, the Hg mine within its immediate neighborhood, and the drainage catchment of the Paglia River has an influence also on Hg speciation, transported mainly in the particulate form by the river system. The extent of Hg contamination has been identified at least 100 km from Abbadia San Salvatore along the Paglia-Tiber River system. Estimated annual Hg mass loads transported by the Paglia River to the Tiber River were about 11 kg yr-1. However, there is evidence that flood events may enhance Hg mobilization in the Paglia River basin, increasing Hg concentrations in stream sediment. The high methyl-Hg/Hg ratio in water in this area is an additional factor of great concern due to the potential harmful effects on human and wildlife health. Results of our studies indicate that the Mt. Amiata region is at present a source of Hg of remarkable environmental concern at the local, regional (Tiber River), and Mediterranean scales. Ongoing studies are aimed to a more detailed quantification of the Hg mass load input to the Mediterranean Sea, and to unravel the processes concerning Hg transport and fluid dynamics.