Flowback verses first-flush: new information on the geochemistry of produced water from mandatory reporting.

Unconventional oil and gas development uses the subsurface injection of large amounts of a variety of industrial chemicals, and there are concerns about the return of these chemical to the surface with water produced with oil and gas from stimulated wells. Produced water, including any flowback of injected fluids, must be managed so as to protect human health and the environment, and understanding the chemistry of produced water from stimulated wells is necessary to ensure the safe management of produced water. In 2014, California instituted mandatory reporting for all well stimulations, including sampling produced water two times and comprehensive chemical characterization of fluids injected and fluids recovered from stimulated wells. In this study, we analyzed data from mandatory reporting with the objective of closing previously identified data gaps concerning oil-field chemical practices and the nature of flowback and produced water from stimulated wells. It was found that the plug-flow conceptual model of flowback developed in shale formations, where salinity increases over time as produced water is extracted, was not appropriate for characterizing produced water from unconventional wells in these oil reservoirs, which are predominately diatomite and sandstones. In these formations stimulation caused a "first-flush" phenomena, where salts and metals were initially high and then decreased in concentration over time, as more produced water was extracted. Although widely applied to meet regulatory requirements, total carbohydrate measurement was not found to be a good chemical indicator of hydraulic fracturing flowback. Mandatory reporting closed data-gaps concerning chemical use, provided new information on acid treatments, and allowed more detailed analysis of hydraulic fracturing practices, including comparison of water use by geological formation.

Comparison of chemical-use between hydraulic fracturing, acidizing, and routine oil and gas development.

The potential hazards and risks associated with well-stimulation in unconventional oil and gas development (hydraulic fracturing, acid fracturing, and matrix acidizing) have been investigated and evaluated and federal and state regulations requiring chemical disclosure for well-stimulation have been implemented as part of an overall risk management strategy for unconventional oil and gas development. Similar evaluations for chemicals used in other routine oil and gas development activities, such as maintenance acidizing, gravel packing, and well drilling, have not been previously conducted, in part due to a lack of reliable information concerning on-field chemical-use. In this study, we compare chemical-use between routine activities and the more closely regulated well-stimulation activities using data collected by the South Coast Air Quality Monitoring District (SCAQMD), which mandates the reporting of both unconventional and routine on-field chemical-use for parts of Southern California. Analysis of this data shows that there is significant overlap in chemical-use between so-called unconventional activities and routine activities conducted for well maintenance, well-completion, or rework. A comparison within the SCAQMD shows a significant overlap between both types and amounts of chemicals used for well-stimulation treatments included under State mandatory-disclosure regulations and routine treatments that are not included under State regulations. A comparison between SCAQMD chemical-use for routine treatments and state-wide chemical-use for hydraulic fracturing also showed close similarity in chemical-use between activities covered under chemical disclosure requirements (e.g. hydraulic fracturing) and many other oil and gas field activities. The results of this study indicate regulations and risk assessments focused exclusively on chemicals used in well-stimulation activities may underestimate potential hazard or risk from overall oil field chemical-use.

Identifying chemicals of concern in hydraulic fracturing fluids used for oil production.

Chemical additives used for hydraulic fracturing and matrix acidizing of oil reservoirs were reviewed and priority chemicals of concern needing further environmental risk assessment, treatment demonstration, or evaluation of occupational hazards were identified. We evaluated chemical additives used for well stimulation in California, the third largest oil producing state in the USA, by the mass and frequency of use, as well as toxicity. The most frequently used chemical additives in oil development were gelling agents, cross-linkers, breakers, clay control agents, iron and scale control agents, corrosion inhibitors, biocides, and various impurities and product stabilizers used as part of commercial mixtures. Hydrochloric and hydrofluoric acids, used for matrix acidizing and other purposes, were reported infrequently. A large number and mass of solvents and surface active agents were used, including quaternary ammonia compounds (QACs) and nonionic surfactants. Acute toxicity was evaluated and many chemicals with low hazard to mammals were identified as potentially hazardous to aquatic environments. Based on an analysis of quantities used, toxicity, and lack of adequate hazard evaluation, QACs, biocides, and corrosion inhibitors were identified as priority chemicals of concern that deserve further investigation.

Physical-chemical evaluation of hydraulic fracturing chemicals in the context of produced water treatment.

Produced water is a significant waste stream that can be treated and reused; however, the removal of production chemicals-such as those added in hydraulic fracturing-must be addressed. One motivation for treating and reusing produced water is that current disposal methods-typically consisting of deep well injection and percolation in infiltration pits-are being limited. Furthermore, oil and gas production often occurs in arid regions where there is demand for new water sources. In this paper, hydraulic fracturing chemical additive data from California are used as a case study where physical-chemical and biodegradation data are summarized and used to screen for appropriate produced water treatment technologies. The data indicate that hydraulic fracturing chemicals are largely treatable; however, data are missing for 24 of the 193 chemical additives identified. More than one-third of organic chemicals have data indicating biodegradability, suggesting biological treatment would be effective. Adsorption-based methods and partitioning of chemicals into oil for subsequent separation is expected to be effective for approximately one-third of chemicals. Volatilization-based treatment methods (e.g. air stripping) will only be effective for approximately 10% of chemicals. Reverse osmosis is a good catch-all with over 70% of organic chemicals expected to be removed efficiently. Other technologies such as electrocoagulation and advanced oxidation are promising but lack demonstration. Chemicals of most concern due to prevalence, toxicity, and lack of data include propargyl alcohol, 2-mercaptoethyl alcohol, tetrakis hydroxymethyl-phosphonium sulfate, thioglycolic acid, 2-bromo-3-nitrilopropionamide, formaldehyde polymers, polymers of acrylic acid, quaternary ammonium compounds, and surfactants (e.g. ethoxylated alcohols). Future studies should examine the fate of hydraulic fracturing chemicals in produced water treatment trains to demonstrate removal and clarify interactions between upstream and downstream processes.

Pairing high-frequency data with a link-node model to manage dissolved oxygen impairment in a dredged estuary.

High-frequency data and a link-node model were used to investigate the relative importance of mass loads of oxygen-demanding substances and channel geometry on recurrent low dissolved oxygen (DO) in the San Joaquin River Estuary in California. The model was calibrated using 6 years of data. The calibrated model was then used to determine the significance of the following factors on low DO: excavation of the river to allow navigation of large vessels, non-point source pollution from the agricultural watershed, effluent from a wastewater treatment plant, and non-point source pollution from an urban area. An alternative metric for low DO, excess net oxygen demand (ENOD), was applied to better characterize DO impairment. Model results indicate that the dredged ship channel had the most significant effect on DO (62 % fewer predicted hourly DO violations), followed by mass load inputs from the watershed (52 % fewer predicted hourly DO violations). Model results suggest that elimination of any one factor will not completely resolve DO impairment and that continued use of supplemental aeration is warranted. Calculation of ENOD proved more informative than the sole use of DO. Application of the simple model allowed for interpretation of the extensive data collected. The current monitoring program could be enhanced by additional monitoring stations that would provide better volumetric estimates of low DO.

Treatment of oil-water emulsion from the machinery industry by Fenton's reagent.

An oil-water emulsion from the machinery industry was treated using Fenton's reagent. The objective was to reduce the high chemical oxygen demand (COD) of this waste stream so that it would meet the COD effluent limit of Chinese Standard JS-7740-95. The optimal [H2O2]/[Fe2+] ratio for COD removal was 3. An orthogonal experimental design was developed based on the optimal [H2O2]/[Fe2+] ratio to evaluate the significance of four parameters relevant to the treatment process, namely, H2O2 dosage, initial pH, oxidation time and coagulation pH. The influence of the four parameters on COD removal efficiency decreased as follows: H2O2 dosage>oxidation time>coagulation pH>initial pH. The COD removal efficiency was further investigated based on the most important single-factor parameter, which was H2O2 dosage, as discovered in the orthogonal test. A well-fitted empirical correlation was obtained from the single-factor analysis and up to 98% COD removal was attained using 50 mM H2O2. Using the doses and conditions identified in this study, the treated oil-water emulsion can be discharged according to Chinese Standard JS-7740-95.

Temperature and injection water source influence microbial community structure in four Alaskan North Slope hydrocarbon reservoirs.

A fundamental knowledge of microbial community structure in petroleum reservoirs can improve predictive modeling of these environments. We used hydrocarbon profiles, stable isotopes, and high-density DNA microarray analysis to characterize microbial communities in produced water from four Alaskan North Slope hydrocarbon reservoirs. Produced fluids from Schrader Bluff (24-27°C), Kuparuk (47-70°C), Sag River (80°C), and Ivishak (80-83°C) reservoirs were collected, with paired soured/non-soured wells sampled from Kuparuk and Ivishak. Chemical and stable isotope data suggested Schrader Bluff had substantial biogenic methane, whereas methane was mostly thermogenic in deeper reservoirs. Acetoclastic methanogens (Methanosaeta) were most prominent in Schrader Bluff samples, and the combined δD and δ(13)C values of methane also indicated acetoclastic methanogenesis could be a primary route for biogenic methane. Conversely, hydrogenotrophic methanogens (e.g., Methanobacteriaceae) and sulfide-producing Archaeoglobus and Thermococcus were more prominent in Kuparuk samples. Sulfide-producing microbes were detected in all reservoirs, uncoupled from souring status (e.g., the non-soured Kuparuk samples had higher relative abundances of many sulfate-reducers compared to the soured sample, suggesting sulfate-reducers may be living fermentatively/syntrophically when sulfate is limited). Sulfate abundance via long-term seawater injection resulted in greater relative abundances of Desulfonauticus, Desulfomicrobium, and Desulfuromonas in the soured Ivishak well compared to the non-soured well. In the non-soured Ivishak sample, several taxa affiliated with Thermoanaerobacter and Halomonas predominated. Archaea were not detected in the deepest reservoirs. Functional group taxa differed in relative abundance among reservoirs, likely reflecting differing thermal and/or geochemical influences.

Physical, chemical, and biological characteristics of compounds used in hydraulic fracturing.

Hydraulic fracturing (HF), a method to enhance oil and gas production, has become increasingly common throughout the U.S. As such, it is important to characterize the chemicals found in HF fluids to evaluate potential environmental fate, including fate in treatment systems, and human health impacts. Eighty-one common HF chemical additives were identified and categorized according to their functions. Physical and chemical characteristics of these additives were determined using publicly available chemical information databases. Fifty-five of the compounds are organic and twenty-seven of these are considered readily or inherently biodegradable. Seventeen chemicals have high theoretical chemical oxygen demand and are used in concentrations that present potential treatment challenges. Most of the HF chemicals evaluated are non-toxic or of low toxicity and only three are classified as Category 2 oral toxins according to standards in the Globally Harmonized System of Classification and Labeling of Chemicals; however, toxicity information was not located for thirty of the HF chemicals evaluated. Volatilization is not expected to be a significant exposure pathway for most HF chemicals. Gaps in toxicity and other chemical properties suggest deficiencies in the current state of knowledge, highlighting the need for further assessment to understand potential issues associated with HF chemicals in the environment.

Metagenomics reveals sediment microbial community response to Deepwater Horizon oil spill.

The Deepwater Horizon (DWH) oil spill in the spring of 2010 resulted in an input of ∼4.1 million barrels of oil to the Gulf of Mexico; >22% of this oil is unaccounted for, with unknown environmental consequences. Here we investigated the impact of oil deposition on microbial communities in surface sediments collected at 64 sites by targeted sequencing of 16S rRNA genes, shotgun metagenomic sequencing of 14 of these samples and mineralization experiments using (14)C-labeled model substrates. The 16S rRNA gene data indicated that the most heavily oil-impacted sediments were enriched in an uncultured Gammaproteobacterium and a Colwellia species, both of which were highly similar to sequences in the DWH deep-sea hydrocarbon plume. The primary drivers in structuring the microbial community were nitrogen and hydrocarbons. Annotation of unassembled metagenomic data revealed the most abundant hydrocarbon degradation pathway encoded genes involved in degrading aliphatic and simple aromatics via butane monooxygenase. The activity of key hydrocarbon degradation pathways by sediment microbes was confirmed by determining the mineralization of (14)C-labeled model substrates in the following order: propylene glycol, dodecane, toluene and phenanthrene. Further, analysis of metagenomic sequence data revealed an increase in abundance of genes involved in denitrification pathways in samples that exceeded the Environmental Protection Agency (EPA)'s benchmarks for polycyclic aromatic hydrocarbons (PAHs) compared with those that did not. Importantly, these data demonstrate that the indigenous sediment microbiota contributed an important ecosystem service for remediation of oil in the Gulf. However, PAHs were more recalcitrant to degradation, and their persistence could have deleterious impacts on the sediment ecosystem.

Use of continuous and grab sample data for calculating total maximum daily load (TMDL) in agricultural watersheds.

Measuring the discharge of diffuse pollution from agricultural watersheds presents unique challenges. Flows in agricultural watersheds, particularly in Mediterranean climates, can be predominately irrigation runoff and exhibit large diurnal fluctuation in both volume and concentration. Flow and pollutant concentrations in these smaller watersheds dominated by human activity do not conform to a normal distribution and it is not clear if parametric methods are appropriate or accurate for load calculations. The objective of this study was to compare the accuracy of five load estimation methods to calculate pollutant loads from agricultural watersheds. Calculation of loads using results from discrete (grab) samples was compared with the true-load computed using in situ continuous monitoring measurements. A new method is introduced that uses a non-parametric measure of central tendency (the median) to calculate loads (median-load). The median-load method was compared to more commonly used parametric estimation methods which rely on using the mean as a measure of central tendency (mean-load and daily-load), a method that utilizes the total flow volume (volume-load), and a method that uses measure of flow at the time of sampling (instantaneous-load). Using measurements from ten watersheds in the San Joaquin Valley of California, the average percent error compared to the true-load for total dissolved solids (TDS) was 7.3% for the median-load, 6.9% for the mean-load, 6.9% for the volume-load, 16.9% for the instantaneous-load, and 18.7% for the daily-load methods of calculation. The results of this study show that parametric methods are surprisingly accurate, even for data that have starkly non-normal distributions and are highly skewed.

Performance of sanitary sewer collection system odour control devices operating in diverse conditions.

Controlling odours from sanitary sewer systems is challenging as a result of the expansive nature of these systems. Addition of oxidizing chemicals is often practiced as a mitigation strategy. One alternative is to remove odorous compounds in the gases vented from manholes using adsorptive media. In this study, odour control devices located at manholes were observed to determine the ability of these systems to reduce hydrogen sulphide from vented gases. The odour control devices incorporated pressure regulation to control gas flow out of manhole covers and adsorptive media to remove hydrogen sulphide in the vented gases prior to release. Pressure regulation was accomplished using a variable volume bladder and two pressure relief valves that permitted gas flow when pressures exceeded 1.3 to 2.5 cm water column. The reduction in gas flow vented from manholes was intended to extend the service life of the adsorptive media, as compared with odour control devices that do not incorporate pressure modulation. Devices were deployed at four locations and three adsorptive media were tested. Although measured collection system hydrogen sulphide concentrations varied from zero to over 1,000 ppm, the removal rates observed using odour control devices were typically above 90%. The lower removal rates observed at one of the sites (50.5 ± 36.1%) appeared related to high gas flow rates being emitted at this location. Activated carbon was used in most of the tests, although use of iron media resulted in the highest removal observed: 97.8 ± 3.6%. The expected service life of the adsorptive media contained within the odour control devices is a function of site-specific hydrogen sulphide concentrations and gas flow rates. The units used in this study were in service for more than 8 to 12 months prior to requiring media replacement.

Succession of hydrocarbon-degrading bacteria in the aftermath of the deepwater horizon oil spill in the gulf of Mexico.

The Deepwater Horizon oil spill produced large subsurface plumes of dispersed oil and gas in the Gulf of Mexico that stimulated growth of psychrophilic, hydrocarbon degrading bacteria. We tracked succession of plume bacteria before, during and after the 83-day spill to determine the microbial response and biodegradation potential throughout the incident. Dominant bacteria shifted substantially over time and were dependent on relative quantities of different hydrocarbon fractions. Unmitigated flow from the wellhead early in the spill resulted in the highest proportions of n-alkanes and cycloalkanes at depth and corresponded with dominance by Oceanospirillaceae and Pseudomonas. Once partial capture of oil and gas began 43 days into the spill, petroleum hydrocarbons decreased, the fraction of aromatic hydrocarbons increased, and Colwellia, Cycloclasticus, and Pseudoalteromonas increased in dominance. Enrichment of Methylomonas coincided with positive shifts in the δ(13)C values of methane in the plume and indicated significant methane oxidation occurred earlier than previously reported. Anomalous oxygen depressions persisted at plume depths for over six weeks after well shut-in and were likely caused by common marine heterotrophs associated with degradation of high-molecular-weight organic matter, including Methylophaga. Multiple hydrocarbon-degrading bacteria operated simultaneously throughout the spill, but their relative importance was controlled by changes in hydrocarbon supply.

Impact of co-digestion on existing salt and nutrient mass balances for a full-scale dairy energy project.

Anaerobic digestion of manure and other agricultural waste streams with subsequent energy production can result in more sustainable dairy operations; however, importation of digester feedstocks onto dairy farms alters previously established carbon, nutrient, and salinity mass balances. Salt and nutrient mass balance must be maintained to avoid groundwater contamination and salination. To better understand salt and nutrient contributions of imported methane-producing substrates, a mass balance for a full-scale dairy biomass energy project was developed for solids, carbon, nitrogen, sulfur, phosphorus, chloride, and potassium. Digester feedstocks, consisting of thickened manure flush-water slurry, screened manure solids, sudan grass silage, and feed-waste, were tracked separately in the mass balance. The error in mass balance closure for most elements was less than 5%. Manure contributed 69.2% of influent dry matter while contributing 77.7% of nitrogen, 90.9% of sulfur, and 73.4% of phosphorus. Sudan grass silage contributed high quantities of chloride and potassium, 33.3% and 43.4%, respectively, relative to the dry matter contribution of 22.3%. Five potential off-site co-digestates (egg waste, grape pomace, milk waste, pasta waste, whey wastewater) were evaluated for anaerobic digestion based on salt and nutrient content in addition to bio-methane potential. Egg waste and wine grape pomace appeared the most promising co-digestates due to their high methane potentials relative to bulk volume. Increasing power production from the current rate of 369 kW to the design value of 710 kW would require co-digestion with either 26800 L d(-1) egg waste or 60900 kg d(-1) grape pomace. However, importation of egg waste would more than double nitrogen loading, resulting in an increase of 172% above the baseline while co-digestion with grape pomace would increase potassium by 279%. Careful selection of imported co-digestates and management of digester effluent is required to manage salt and nutrient mass loadings and reduce groundwater impacts.

Biotransformation of chlorpyrifos in riparian wetlands in agricultural watersheds: implications for wetland management.

Biodegradation of the organophosphate insecticide chlorpyrifos (O,O-diethyl O-(3,5,6-trichloropyridin-2-yl) phosphorothioate) in sediments from wetlands and agricultural drains in San Joaquin Valley, CA was investigated. Sediments were collected monthly, spiked with chlorpyrifos, and rates of chlorpyrifos degradation were measured using a standardized aerobic biodegradation assay. Phosphoesterase enzyme activities were measured and phosphotriesterase activity was related to observed biodegradation kinetics. First-order biodegradation rates varied between 0.02 and 0.69 day(-1), after accounting for abiotic losses. The average rate of abiotic chlorpyrifos hydrolysis was 0.02 d(-1) at pH 7.2 and 30 °C. Sediments from the site exhibiting the highest chlorpyrifos degradation capacity were incubated under anaerobic conditions to assess the effect of redox conditions on degradation rates. Half-lives were 5 and 92 days under aerobic and anaerobic conditions, respectively. There was a consistent decrease in observed biodegradation rates at one site due to permanently flooded conditions prevailing during one sampling year. These results suggest that wetland management strategies such as allowing a wet-dry cycle could enhance degradation rates. There was significant correlation between phosphotriesterase (PTE) activity and the chlorpyrifos biotransformation rates, with this relationship varying among sites. PTE activities may be useful as an indicator of biodegradation potential with reference to the previously established site-specific correlations.

Sizing mitigation wetlands in agricultural watersheds.

In this study, we investigated use of microcosms to supplement field studies for establishing the size of wetlands required to mitigate nitrate pollution in agricultural watersheds. Wetlands investigated in this study were located in San Joaquin Valley (California, USA) and demonstrated mean nitrate-nitrogen mass removal efficiencies ranging between 10 and 34%. Mean areal nitrate removal rates (J) ranged from 142 to 380 mg-N m(-2) d(-1). First-order rate constants determined from field data had a high variance, with confidence intervals greater than 57% of mean values. Sediments and rooted plants from one site were placed in a flow-through microcosm and measurements of nitrate removal kinetics were made and compared with field results. The apparent half-saturation constant (K(m)) and maximum removal rate (J(max)) for nitrate-nitrogen were 43.8 mg/L and 4.11 g m(-2) d(-1) in the microcosm. The first-order rate constant from the microcosm (10.4 cm d(-1)) was in close agreement with the value for the field site (11.9 cm d(-1)) and had a confidence interval of less than 16%. Using this improved first-order rate constant, it was determined that between 1.3 and 3.6% of the land in the watershed should be managed as mitigation wetland, with the area required dependent on the level of nitrate reduction desired and how closely the wetland design approximates plug-flow.

Distribution of hydrocarbons released during the 2010 MC252 oil spill in deep offshore waters.

The explosion of the Deepwater Horizon oil platform on April 20th, 2010 resulted in the second largest oil spill in history. The distribution and chemical composition of hydrocarbons within a 45 km radius of the blowout was investigated. All available certified hydrocarbon data were acquired from NOAA and BP. The distribution of hydrocarbons was found to be dispersed over a wider area in subsurface waters than previously predicted or reported. A deepwater hydrocarbon plume predicted by models was verified and additional plumes were identified. Because the samples were not collected systematically, there is still some question about the presence and persistence of an 865 m depth plume predicted by models. Water soluble compounds were extracted from the rising oil in deepwater, and were found at potentially toxic levels outside of areas previously reported to contain hydrocarbons. Application of subsurface dispersants was found to increase hydrocarbon concentration in subsurface waters.

Deep-sea oil plume enriches indigenous oil-degrading bacteria.

The biological effects and expected fate of the vast amount of oil in the Gulf of Mexico from the Deepwater Horizon blowout are unknown owing to the depth and magnitude of this event. Here, we report that the dispersed hydrocarbon plume stimulated deep-sea indigenous γ-Proteobacteria that are closely related to known petroleum degraders. Hydrocarbon-degrading genes coincided with the concentration of various oil contaminants. Changes in hydrocarbon composition with distance from the source and incubation experiments with environmental isolates demonstrated faster-than-expected hydrocarbon biodegradation rates at 5°C. Based on these results, the potential exists for intrinsic bioremediation of the oil plume in the deep-water column without substantial oxygen drawdown.

Disinfection byproduct formation potentials of wetlands, agricultural drains, and rivers and the effect of biodegradation on trihalomethane precursors.

Trihalomethane (THM) precursors are a significant problem in the San Joaquin River (SJR) watershed, an important source of drinking water for >20 million people. Trihalomethane precursors diminish drinking water quality and are formed during natural decomposition of organic matter in aquatic systems. This study sought to identify sources of chlorine-reactive dissolved organic carbon (DOC) in the SJR watershed and to determine if wetlands were more important sources of THM precursors than nearby rivers and agricultural drains. The effects of biodegradation on DOC quality and quantity were investigated and analyzed across drainage type. Results show wetland drainage contained comparable bromide concentrations and organic carbon aromaticity but contained more than two times the average DOC concentrations found in agricultural drains and rivers. Wetland DOC did not have an increased propensity to form THMs when compared with the other drainage types, despite significantly higher wetland formation potentials. The higher formation potentials measured in wetland drainages were attributed to higher DOC concentrations; the positive correlation found between DOC and trihalomethane formation potentials (THMFPs) and the significantly higher wetland DOC concentrations suggest that increased wetland restoration could result in increased THMFPs in the SJR watershed. Wetland THM precursors were more resistant to biodegradation than THM precursors from agricultural and river samples. Results suggest that THM precursors in the SJR were from algae and were biodegraded.

Partitioning of chlorpyrifos to soil and plants in vegetated agricultural drainage ditches.

Constructed wetlands and vegetated agricultural drainage ditches (VADD) have been proposed as structural best management practices for the mitigation of chlorpyrifos contamination in agriculturally dominated watersheds. Sorption to soil and submergent aquatic plants has been measured as an important sink for chlorpyrifos; however, sorption to emergent plants has not been well characterized. Sorption isotherms for two soils and five emergent plants were determined by batch equilibrium technique. Sorption to whole plant stems (K(d)=570-1300 L kg(-1)) was more than 10 times higher than to soil (K(d)=40-71 L kg(-1)). Chopped plant material had K(d) values 7.6-96.2% greater than whole stems. Wetland plants with high internal surface area due to porous tissues had greater linear partitioning coefficients than terrestrial plants with a hollow structure. Chlorpyrifos sorption reached pseudo-equilibrium rapidly, indicating that partitioning will be an important mechanism in vegetated natural treatment systems for mitigating peak concentrations in surface waters and allowing time for attenuation by slower degradation reactions.

Ranking methods to set restoration and remediation priorities on a watershed scale.

The establishment of a total maximum daily load (TMDL) is part of management process that results in the institution of watershed-based controls of otherwise unregulated sources of pollution. In California (USA), the implementation of a TMDL is driven forward in a process where watershed stakeholders are expected to cooperate on actions needed to improve ecosystem health. In the TMDL process, methods are needed for synthesizing complex scientific data into actionable management information. Where pollutant load analysis may be misleading or perceived as unfair, non-parametric statistical methods can be applied to flow and water quality data to guide the selection of drainages for remediation. The calculation of normalized rank means (NRMs) for flow and water quality can be used to set priorities for the implementation of TMDL management actions. Drainages can be classified into one of four categories (quadrants) based on the relationship between flow and water quality NRMs. Drainages can be included or excluded from management action based on their quadrant classification. Although there are many possible alternative approaches, this "quadrant analysis" is suggested as a scientifically rigorous methods for identifying priority watersheds in the often contentious, stakeholder driven TMDL implementation process.