Satellite Remote Sensing: A Tool to Support Harmful Algal Bloom Monitoring and Recreational Health Advisories in a California Reservoir.

Cyanobacterial harmful algal blooms (cyanoHABs) can harm people, animals, and affect consumptive and recreational use of inland waters. Monitoring cyanoHABs is often limited. However, chlorophyll-a (chl-a) is a common water quality metric and has been shown to have a relationship with cyanobacteria. The World Health Organization (WHO) recently updated their previous 1999 cyanoHAB guidance values (GVs) to be more practical by basing the GVs on chl-a concentration rather than cyanobacterial counts. This creates an opportunity for widespread cyanoHAB monitoring based on chl-a proxies, with satellite remote sensing (SRS) being a potentially powerful tool. We used Sentinel-2 (S2) and Sentinel-3 (S3) to map chl-a and cyanobacteria, respectively, classified chl-a values according to WHO GVs, and then compared them to cyanotoxin advisories issued by the California Department of Water Resources (DWR) at San Luis Reservoir, key infrastructure in California's water system. We found reasonably high rates of total agreement between advisories by DWR and SRS, however rates of agreement varied for S2 based on algorithm. Total agreement was 83% for S3, and 52%-79% for S2. False positive and false negative rates for S3 were 12% and 23%, respectively. S2 had 12%-80% false positive rate and 0%-38% false negative rate, depending on algorithm. Using SRS-based chl-a GVs as an early indicator for possible exposure advisories and as a trigger for in situ sampling may be effective to improve public health warnings. Implementing SRS for cyanoHAB monitoring could fill temporal data gaps and provide greater spatial information not available from in situ measurements alone.

Plankton population dynamics and methylmercury bioaccumulation in the pelagic food web of mine-impacted surface water reservoirs.

Thermal stratification of reservoirs can lead to anaerobic conditions that facilitate the microbial conversion of mercury (Hg) to neurotoxic and bioaccumulative methylmercury (MeHg). But MeHg production is just the first step in a complex set of processes that affect MeHg in fish. Of particular relevance is uptake into suspended particulate matter (SPM) and zooplankton at the base of the pelagic food web. We assessed plankton dynamics and Hg uptake into the pelagic food web of four Hg-impaired California water reservoirs. Combining water chemistry, plankton taxonomy, and stable carbon (C) and nitrogen (N) isotope values of SPM and zooplankton samples, we investigated differences among the reservoirs that may contribute to differing patterns in MeHg bioaccumulation. Methylmercury accumulated in SPM during the spring and summer seasons. Percent MeHg (MeHg/Hg*100%) in SPM was negatively associated with δ15N values, suggesting that "fresh" algal biomass could support the production and bioaccumulation of MeHg. Zooplankton δ13C values were correlated with SPM δ13C values in the epilimnion, suggesting that zooplankton primarily feed in surface waters. However, zooplankton MeHg was poorly associated with MeHg in SPM. Our results demonstrate seasonal patterns in biological MeHg uptake and how multiple data sources can help constrain the drivers of MeHg bioaccumulation. Supplementary Information: The online version contains supplementary material available at 10.1007/s10750-022-05018-0.

Effects of mercury, organic carbon, and microbial inhibition on methylmercury cycling at the profundal sediment-water interface of a sulfate-rich hypereutrophic reservoir.

Methylmercury (MeHg) produced by anaerobic bacteria in lakes and reservoirs, poses a threat to ecosystem and human health due to its ability to bioaccumulate in aquatic food webs. This study used 48-hr microcosm incubations of profundal sediment and bottom water from a sulfate-rich, hypereutrophic reservoir to assess seasonal patterns of MeHg cycling under various treatments. Treatments included addition of air, Hg(II), organic carbon, and microbial inhibitors. Both aeration and sodium molybdate, a sulfate-reducing bacteria (SRB) inhibitor, generally decreased MeHg concentration in microcosm water, likely by inhibiting SRB activity. The methanogenic inhibitor bromoethanesulfonate increased MeHg concentration 2- to 4- fold, suggesting that methanogens were potent demethylators. Pyruvate increased MeHg concentration under moderately reduced conditions, likely by stimulating SRB, but decreased it under highly reduced conditions, likely by stimulating methanogens. Acetate increased MeHg concentration, likely due to the stimulation of acetotrophic SRB. Results suggest that iron-reducing bacteria (IRB) were not especially prominent methylators and MeHg production at the sediment-water interface is elevated under moderately reduced conditions corresponding with SRB activity. In contrast, it is suppressed under oxic conditions due to low SRB activity, and under highly reduced conditions (<-100 mV) due to enhanced demethylation by methanogens.

Effects of hypolimnetic oxygenation on fish tissue mercury in reservoirs near the new Almaden Mining District, California, USA.

Almaden, Calero, and Guadalupe reservoirs (San Jose, CA, USA) are small (<13 million m3) surface water reservoirs polluted by the former New Almaden Mining District, North America's most productive historical mercury (Hg) mine. Stevens Creek Reservoir (Cupertino, CA, USA) also has elevated fish Hg concentrations, but no historical mining source. We report a 15-year dataset to evaluate the effectiveness of line diffuser hypolimnetic oxygenation systems (HOSs) in reducing methylmercury (MeHg) concentrations in reservoir water and fish after four consecutive years of operation. HOSs were installed in each reservoir to increase dissolved oxygen concentrations in bottom water, thereby suppressing the activity of anaerobic bacteria (e.g., sulfate-reducing bacteria) known to produce MeHg. Before HOS operation, MeHg concentrations increased in bottom waters of all four reservoirs during periods of thermal stratification and profundal hypoxia. MeHg concentrations decreased significantly in bottom waters during HOS operation, with mean reductions of 63%-85% below pre-oxygenation concentrations. However, MeHg concentrations were unchanged or increased in surface waters. This could be the result of enhanced mixing between surface and bottom waters as a result of line diffuser oxygenation, or continued Hg methylation occurring in the oxic water column and littoral sediments. Despite little change in whole water column MeHg concentrations, we observed modest but significant declining trends in fish tissue Hg in Guadalupe and Stevens Creek reservoirs. Results suggest that oxygenation, rather than directly lowering MeHg in water, may have mixed nutrients into surface waters, thereby enhancing primary productivity and indirectly affecting Hg bioaccumulation by diluting concentrations in phytoplankton.

Monitoring of Airborne Mercury: Comparison of Different Techniques in the Monte Amiata District, Southern Tuscany, Italy.

In the present study, mercury (Hg) concentrations were investigated in lichens (Flavoparmelia caperata (L.) Hale, Parmelia saxatilis (L.) Ach., and Xanthoria parietina (L.) Th.Fr.) collected in the surrounding of the dismissed Abbadia San Salvatore Hg mine (Monte Amiata district, Italy). Results were integrated with Hg concentrations in tree barks and literature data of gaseous Hg levels determined by passive air samplers (PASs) in the same area. The ultimate goal was to compare results obtained by the three monitoring techniques to evaluate potential mismatches. Lichens displayed 180-3600 ng/g Hg, and Hg concentrations decreased exponentially with distance from the mine. Mercury concentration was lower than in Pinus nigra barks at the same site. There was a moderate correlation between Hg in lichen and Hg in bark, suggesting similar mechanisms of Hg uptake and residence times. However, correlation with published gaseous Hg concentrations (PASs) was moderate at best (Kendall Tau = 0.4-0.5, p > 0.05). The differences occurred because a) PASs collected gaseous Hg, whereas lichens and barks also picked up particulate Hg, and b) lichens and bark had a dynamic exchange with the atmosphere. Lichen, bark, and PAS outline different and complementary aspects of airborne Hg content and efficient monitoring programs in contaminated areas would benefit from the integration of data from different techniques.

Mercury removal from municipal secondary effluent with hydrous ferric oxide reactive filtration.

This study evaluated the ability of hydrous ferric oxide reactive filtration (HFO-RF) to remove mercury (Hg) from municipal secondary effluent at four study sites. Pilot HFO-RF systems (136 m3 /day) at two sites demonstrated total Hg concentration removal efficiencies of 96% (inflow/outflow mean total Hg: 43.6/1.6  ng/L) and 80% (4.2/0.8 ng/L). A lightly loaded medium-scale HFO-RF system (950 m3 /day) had a concentration removal efficiency of 53% (0.98/0.46 ng/L) and removed 0.52 mg/day of total Hg and 2.2 µg/day of methyl-Hg. A full-scale HFO-RF system (11,400 m3 /day) yielded a total Hg concentration removal efficiency of 97% (87/2.7 ng/L) and removed an estimated 0.36 kg/year of Hg. Results suggest that the quality of secondary effluent, including dissolved organic matter content, affects achievable minimum total Hg concentrations in effluent from HFO-RF systems. Low HFO-RF effluent concentrations (<1 ng/L) can be expected when treating secondary effluent from suspended-growth biological treatment systems. PRACTITIONER POINTS: Trace levels of mercury in municipal secondary effluent can negatively impact receiving waters. Hydrous ferric oxide reactive filtration (HFO-RF) can remove mercury from municipal secondary effluent to levels below the Great Lakes Initiative discharge standard of 1.3 ng/L. Mercury removal to low concentrations (< 1 ng/L) using HFO-RF appears to be associated with secondary effluents with low dissolved organic matter content. HFO-RF can also remove total phosphorus and turbidity to low concentrations.

Effect of oxygen, nitrate and aluminum addition on methylmercury efflux from mine-impacted reservoir sediment.

Extensive contamination of aquatic ecosystems with mercury (Hg) has led to a growing interest in developing in situ management strategies to repress Hg bioaccumulation in aquatic biota in reservoirs. This study used experimental chamber incubations to assess the impact of three potential treatments, oxygen addition, nitrate addition and aluminum addition, to reduce the flux of toxic methylmercury (MeHg) from profundal reservoir sediment. The study sites, Almaden Lake and Guadalupe Reservoir, are located downstream of the historic New Almaden mining district in Santa Clara Valley, California, USA. In the first experiment (experiment 1), replicate chambers from both sites were incubated sequentially under aerobic and anaerobic conditions. At both sites, mean anaerobic fluxes of MeHg were higher than aerobic fluxes (Almaden: 11.0 vs. -2.3 ng/m2·d; Guadalupe: 22.3 vs 5.5 ng/m2·d), and anaerobic MeHg fluxes correlated with rates of sediment sulfate uptake, highlighting the linkage between MeHg production and microbial sulfate reduction. Under aerobic conditions, sediment from Guadalupe Reservoir released Hg(II), iron and sulfate, suggesting the oxidative dissolution of Hg-bearing sulfide minerals. A follow-up study at Almaden Lake (experiment 2) found that mean MeHg fluxes under aerobic conditions (5 ng/m2·d) and anoxic (nitrate-rich) conditions (1.7 ng/m2·d) were lower than anaerobic conditions (174 ng/m2·d), but aluminum addition had little effect (105 ng/m2·d) on MeHg flux. In both anaerobic and aluminum treated chambers, MeHg flux turned negative during the second half of the incubation, suggesting that highly reduced, sulfidic conditions lowered net methylation, possibly by enhancing demethylation or repressing Hg(II) bioavailability for methylation.

Tracking long-distance atmospheric deposition of trace metal emissions from smelters in the upper Columbia River valley using Pb isotope analysis of lake sediments.

Heavy metal discharge from mining and smelting operations into aquatic ecosystems can cause long-term biological and ecological impacts. The upper Columbia River is highly contaminated with heavy metal wastes from nearby smelting operations in Trail, British Columbia, Canada, and to a lesser extent, Northport (Le Roi smelter), Washington, USA. Airborne emissions from the Trail operations were historically and are currently transported by prevailing winds down the Columbia River canyon, where particulate metals can be deposited into lakes and watersheds. In lakes, sediment cores contain records of past environmental conditions, providing a timeline of fundamental chemical and biological relationships within aquatic ecosystems, including records of airborne metal depositions. We analyzed trace metal concentrations (Ni, Cd, Zn, As, Cu, Sb, Pb, Hg) and Pb isotope compositions of sediment cores from six remote eastern Washington lakes to assess potential sources of atmospheric heavy metal deposition. Sediment cores displayed evidence to support trace metal loading as a direct consequence of smelting operations in Trail. Smelter contamination was detected 144 km downwind of the Trail Smelter. Cd, Sb, Pb (p < 0.001), and to a lesser extent As and Hg (p < 0.05) concentrations were correlated with Pb isotope compositions, suggesting that the Trail operations were likely the main source for these trace metals.

Effects of nitrate addition on water column methylmercury in Occoquan Reservoir, Virginia, USA.

Mercury bioaccumulation in aquatic biota poses a widespread threat to human and environmental health. Methylmercury (MeHg), the toxic form of mercury, tends to build up under anaerobic conditions in the profundal zones of lakes. In this study we performed a two-year assessment of spatial and temporal patterns of dissolved oxygen, nitrate, MeHg, manganese (Mn) and iron (Fe) in Occoquan Reservoir, a large run-of-the-river drinking water reservoir in Virginia, USA. A tributary to the reservoir receives input of nitrate-rich tertiary-treated wastewater that enhances the oxidant capacity of bottom water. Multiple lines of evidence supported the hypothesis that the presences of nitrate and/or oxygen in bottom water correlated with low MeHg in bottom water. Bottom water MeHg was significantly lower in a nitrate-rich tributary (annual mean of 0.05 ng/L in both 2012 and 2013) compared to a nitrate-poor tributary (annual mean of 0.58 ng/L in 2012 and 0.21 ng/L in 2013). The presence of nitrate and oxygen in bottom water corresponded with significantly lower bottom water MeHg at an upstream station in the main reservoir (0.05 versus 0.11 ng/L in 2013). In 2012 the reservoir exhibited a longitudinal gradient with nitrate and oxygen decreasing and MeHg and Mn increasing downstream. In both study years, there was a clear threshold of oxygen equivalent (3-5 mg/L), a metric that combines the oxidant capacity of nitrate and oxygen, above which MeHg (<0.05 ng/L), Mn (<0.3 mg/L) and Fe (<0.5 mg/L) were low. Results indicated that the addition of nitrate-rich tertiary-treated wastewater to the bottom of anaerobic reservoirs can reduce MeHg concentrations, and potentially decrease mercury bioaccumulation, while increasing the safe water yield for potable use.

Black pine (Pinus nigra) barks as biomonitors of airborne mercury pollution.

Tree barks are relevant interfaces between plants and the external environment, and can effectively retain airborne particles and elements at their surface. In this paper we have studied the distribution of mercury (Hg) in soils and in black pine (Pinus nigra) barks from the Mt. Amiata Hg district in southern Tuscany (Italy), where past Hg mining and present-day geothermal power plants affect local atmospheric Hg concentration, posing serious environmental concerns. Barks collected in heavily Hg-polluted areas of the district display the highest Hg concentration ever reported in literature (8.6mg/kg). In comparison, barks of the same species collected in local reference areas and near geothermal power plants show much lower (range 19-803µg/kg) concentrations; even lower concentrations are observed at a "blank" site near the city of Florence (5-98µg/kg). Results show a general decrease of Hg concentration from bark surface inwards, in accordance with a deposition of airborne Hg, with minor contribution from systemic uptake from soils. Preliminary results indicate that bark Hg concentrations are comparable with values reported for lichens in the same areas, suggesting that tree barks may represent an additional useful tool for biomonitoring of airborne Hg.

Potential application of Alcaligenes faecalis strain No. 4 in mitigating ammonia emissions from dairy wastewater.

This research examined the potential mitigation of NH3 emissions from dairy manure via an enhanced aerobic bio-treatment with bacterium Alcaligenes faecalis strain No. 4. The studies were conducted in aerated batch reactors using air and pure oxygen. Aeration with air and oxygen removed approximately 40% and 100% total ammoniacal nitrogen (TAN), respectively. Intermittent oxygenation (every 2 or 4 h) reduced oxygen consumption by 95%, while attaining nearly identical TAN removal to continuous aeration. The results revealed that adequate oxygen supply and supplementing dairy wastewater with carbon are essential for this bioprocess. Based on the nitrogen mass balance, only 4% of TAN was released as NH3 gas, while the majority was retained in either the microbial biomass (58%) or converted to nitrogen gas (36%). The mass balance results reveal high potential for environmentally friendly bio-treatment of dairy wastewater using A. faecalis strain No. 4 with respect to NH3 emissions.

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.

Phosphorus removal in a surface-flow constructed wetland treating agricultural runoff.

Agricultural runoff is a leading source of phosphorus (P) pollution to lakes and streams. The objective of this study was to evaluate P removal dynamics in a constructed treatment wetland (CTW) treating agricultural irrigation return flows. The CTW included a sedimentation basin (SB) followed by two surface-flow wetlands in parallel. Typical retention times and total P (TP) loading were 1.4 d and 50 to 110 g m yr P, respectively, for the SB and 5 to 6 d and 4 to 10 g m yr P, respectively, for wetlands. On the basis of this multiyear study, concentration removal efficiency in the SB averaged 21% for TP and 32% for reactive phosphorus (RP). Concentration removal efficiency in wetlands averaged 37 and 43% for TP and 22 and 33% for RP. Areal first-order removal rates for TP averaged 22 and 31 m yr in wetlands. Total P removal in wetlands exhibited a strong seasonal pattern, with minimum removal in the summer when high temperatures likely enhanced P release from decaying plant biomass. The performance of the CTW was stochastic, with removal unpredictably poorer in some years in part as a result of muskrat bioturbation and plant harvesting. In years before muskrat impacts, concentration removal efficiencies in wetlands were 50% for TP and 65% for RP.

Fecal coliform removal in a lightly loaded surface-flow constructed treatment wetland polishing agricultural runoff.

Constructed treatment wetlands can be an effective and sustainable method to remove pathogens that pose health risks from agricultural runoff. This study evaluated the removal of fecal coliform (FC) from agricultural runoff in a lightly loaded surface-flow treatment wetland prior to discharge to the Yakima River, Washington State, USA. The 1.6 ha system consisted of a sedimentation basin (1.4 d hydraulic retention time) followed by two wetlands (5-6 d hydraulic retention time). FC in inflow ranged from 100 to 1,000 cfu/100 mL. Mean annual FC log-removal in the sedimentation basin was 0.66 ± 0.17 (mean plus/minus standard deviation; n = 7). However, there was a comparable production of FC within the two wetlands where annual log-removal averaged -0.71 ± 0.39 in the north wetland and -0.57 ± 0.17 in the south wetland. FC removal in the sedimentation basin weakly correlated with turbidity removal (R(2) = 0.13, p < 0.01, n = 61), suggesting that settling was an important FC loss mechanism. FC removal in the wetlands negatively correlated with temperature (R(2) = 0.27-0.33, p < 0.01, n = 26) indicating that survival and/or reproduction was an important FC production mechanism. Muskrat colonization in the wetlands in 2007 and 2008 corresponded with a marked increase in FC in wetland outflow. Results suggest that, regardless of the presence of muskrats, sedimentation basins alone are more effective than a combined sedimentation basin-wetland system in removing FC from dilute agricultural runoff.

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.

Water quality in a surface-flow constructed treatment wetland polishing tertiary effluent from a municipal wastewater treatment plant.

Constructed treatment wetlands (CTWs) are unique ecotechnologies that can sustainably treat a range of wastewaters. This study focused on a 0.23 ha vegetated surface-flow CTW polishing nitrate-rich (3-6 mg-N/L) tertiary effluent from a municipal wastewater treatment plant. Water quality was monitored longitudinally in the fall of 2009 and 2010. The CTW cooled water by from around 20 °C to <15 °C in both years. Longitudinal temperature profiles were successfully modeled using an energy balance approach (2009 R(2) = 0.69; 2010 R(2) = 0.92). The magnitude of key model fitting parameters, including albedo (0.1-0.2) and convective transfer coefficient (0.1-0.9 MJ/m(2) d °C), were within ranges reported in the literature. In both years, dissolved oxygen decreased through the wetland from 6-7 mg/L to 3-4 mg/L, yielding an oxygen mass consumption rate of 0.08-0.09 g/m(2) d. Longitudinal nitrate profiles were well represented by the P-k-C* model (2009 R(2) = 0.88; 2010 R(2) = 0.92). First order removal rates were 20.2 m/yr in 2009 and 29.0 m/yr in 2010 at a P value of 6.0. Levels of ammonia and total phosphorus increased negligibly through the wetland, remaining below 0.25 mg/L. This study shows that vegetated surface-flow CTWs are well suited to cool and polish low-BOD nitrate-dominated tertiary effluents with little degradation of other water quality parameters of concern, including phosphorus and ammonia.

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.