Causes of ambient toxicity in the Calleguas Creek watershed of southern California

A combination of toxicity tests, chemical analyses, andToxicity Identification Evaluations (TIEs) were used toinvestigate receiving water toxicity in the Calleguas Creekwatershed of southern California. Studies were conductedfrom 1995 through 1999 at various sites to investigatecauses of temporal variability of toxicity throughout thissystem. Causes of receiving water toxicity varied by siteand species tested. Investigations in the lower watershed(Revolon Slough, Santa Clara Drain, Beardsley Wash)indicated that toxicity of samples to the cladoceran Ceriodaphnia dubia due to elevated concentrations ofthe organophosphate pesticide chlorpyrifos, while causes ofintermittent toxicity to fathead minnows (Pimephalespromelas) and the alga Selanastrum capricornutum wereless clear. Investigations at sites in the middle and upperreaches of the watershed (Arroyo Simi and Conejo Creek)indicated that the pesticide diazinon was the probable causeof receiving water toxicity to Ceriodaphnia. Elevatedammonia was the cause of toxicity to fathead minnows in theupper watershed sites. Results of these and previousstudies suggest that biota are impacted by degraded streamquality from a variety of point and non-point pollutionsources in the Calleguas Creek watershed. Water qualityresource manager's efforts to identify contaminant inputsand implement source control will be improved with thefindings of this study.     

Characterizing agrochemical patterns and effective BMPs for surface waters using mechanistic modeling and GIS

Monitoring programs in the agriculturally intense San Joaquin River Valley of California have periodically found organophosphate (OP) insecticide concentrations, predominantly chlorpyrifos, diazinon and methidathion, at levels high enough to cause mortality for the aquatic invertebrate Ceriodaphnia dubia. These detections are likely the result of off-site movement from treated fields. However, the relative significance and magnitude of off-site transport pathways cannot be readily deduced from monitoring data alone. Therefore, a comprehensive modeling system has been constructed to estimate temporal and spatial pesticide source magnitudes and to follow the pesticide dissipation pathways once in surface water. The USEPA models HSPF and PRZM3 were used for the hydrology and non-point source predictions, respectively. Spray drift was accounted for using the mechanistic model AgDrift. The Orestimba Creek Watershed in the San Joaquin Valley was characterized and used as a typical watershed for this region. Representative transport pathways were ranked and quantified, and numerical implementation of best management practices (BMPs) determined which practice may have the highest likelihood for reducing pesticide loadings. Approximately 85% of the predicted chlorpyrifos mass detected between May 1, 1996, and April 30, 1997 resulted from drift, with the largest contributions coming from walnut orchards immediately adjacent to Orestimba Creek. Various simulated drift mitigation measures suggest chlorpyrifos mass loadings can be decreased by over 90% depending upon the type of mitigation chosen. Imposed drift BMPs should be effective in reducing chlorpyrifos levels found in surface waters of the San Joaquin valley if the Orestimba creek watershed is considered representative of watersheds found in this area of California.     

Impacts of pesticides in a Central California estuary

Recent and past studies have documented the prevalence of pyrethroid and organophosphate pesticides in urban and agricultural watersheds in California. While toxic concentrations of these pesticides have been found in freshwater systems, there has been little research into their impacts in marine receiving waters. Our study investigated pesticide impacts in the Santa Maria River estuary, which provides critical habitat to numerous aquatic, terrestrial, and avian species on the central California coast. Runoff from irrigated agriculture constitutes a significant portion of Santa Maria River flow during most of the year, and a number of studies have documented pesticide occurrence and biological impacts in this watershed. Our study extended into the Santa Maria watershed coastal zone and measured pesticide concentrations throughout the estuary, including the water column and sediments. Biological effects were measured at the organism and community levels. Results of this study suggest the Santa Maria River estuary is impacted by current-use pesticides. The majority of water samples were highly toxic to invertebrates (Ceriodaphnia dubia and Hyalella azteca), and chemistry evidence suggests toxicity was associated with the organophosphate pesticide chlorpyrifos, pyrethroid pesticides, or mixtures of both classes of pesticides. A high percentage of sediment samples were also toxic in this estuary, and sediment toxicity occurred when mixtures of chlorpyrifos and pyrethroid pesticides exceeded established toxicity thresholds. Based on a Relative Benthic Index, Santa Maria estuary stations where benthic macroinvertebrate communities were assessed were degraded. Impacts in the Santa Maria River estuary were likely due to the proximity of this system to Orcutt Creek, the tributary which accounts for most of the flow to the lower Santa Maria River. Water and sediment samples from Orcutt Creek were highly toxic to invertebrates due to mixtures of the same pesticides measured in the estuary. This study suggests that the same pyrethroid and organophosphate pesticides that have been shown to cause water and sediment toxicity in urban and agriculture water bodies throughout California, have the potential to affect estuarine habitats. The results establish baseline data in the Santa Maria River estuary to allow evaluation of ecosystem improvement as management initiatives to reduce pesticide runoff are implemented in this watershed.     

Vegetated ditches as a management practice in irrigated alfalfa

The organophosphate (OP) insecticides diazinon and chlorpyrifos have been frequently detected in the San Joaquin River, California, USA. Irrigation tail waters are a significant source of OP pesticides in the watershed. This study tested several management practices for reducing offsite movement of chlorpyrifos to surface water from flood irrigated alfalfa. Management practices evaluated include (1) a constructed, vegetated irrigation tailwater return ditch and (2) increased lag time between chlorpyrifos application and start of flood irrigation. Chlorpyrifos concentrations in whole-water samples of irrigation runoff were variable and ranged from 0.22 mug/l to a maximum of 1.67 mug/l. The median concentration reduction at the end of a 200 m vegetated ditch was 38% compared to 1% in an adjacent conventional tail water ditch. Runoff data collected represented first flush runoff from sets that were irrigated between 48 and 144 h after chlorpyrifos application. There was no consistent effect of irrigation lag time on chlorpyrifos concentration in tailwater for lag times of up to 144 h. Consequently these data indicate that delayed irrigation is not an effective management practice for reducing chlorpyrifos off-site movement to surface water in California flood irrigated alfalfa.     

Pesticide concentrations in water and sediment and associated invertebrate toxicity in Del Puerto and Orestimba Creeks, California, 2007�C2008

The California??s San Joaquin River and its tributaries including Orestimba (ORC) and Del Puerto (DPC) Creeks are listed on the 2006 US EPA Clean Water Act §303(d) list for pesticide impairment. From December 2007 through June 2008, water and sediment samples were collected from both creeks in Stanislaus County to determine concentrations of organophosphorus (OP) and pyrethroid insecticides and to identify toxicity to Ceriodaphnia dubia and Hyalella azteca. OPs were detected in almost half (10 of 21) of the water samples, at concentrations from 0.005 to 0.912 ??g L^???1. Diazinon was the most frequently detected OP, followed by chlorpyrifos and dimethoate. Two water samples were toxic to C. dubia; based on median lethal concentrations (LC₅₀), chlorpyrifos was likely the cause of this toxicity. Pyrethroids were detected more frequently in sediment samples (18 detections) than in water samples (three detections). Pyrethroid concentrations in water samples ranged from 0.005 to 0.021 ??g L^???1. These concentrations were well below reported C. dubia LC₅₀s, and toxicity was not observed in laboratory bioassays. Cyfluthrin, bifenthrin, esfenvalerate, and ??-cyhalothrin were detected in sediment samples at concentrations ranging from 1.0 to 74.4 ng g^???1, dry weight. At DPC, all but one sediment sample caused 100% toxicity to H. azteca. Based on estimated toxicity units (TUs), bifenthrin was likely responsible for this toxicity and ??-cyhalothrin also contributed. At ORC, survival of H. azteca was significantly reduced in four of the 11 sediment samples. However, pyrethroids were detected in only two of these samples. Based on TUs, bifenthrin and ??-cyhalothrin likely contributed to the toxicity.     

Spatial Relationships Between Water Quality and Pesticide Application Rates in Agricultural Watersheds

Pesticide applications to agricultural lands in California, USA, are reported to a central data base, while data on water and sediment quality are collected by a number of monitoring programs. Data from both sources are geo-referenced, allowing spatial analysis of relationships between pesticide application rates and the chemical and biological condition of water bodies. This study collected data from 12 watersheds, selected to represent a range of pesticide usage. Water quality parameters were measured during six surveys of stream sites receiving runoff from the selected watershed areas. This study had three objectives: to evaluate the usefulness of pesticide application data in selecting regional monitoring sites, to provide information for generating and testing hypotheses about pesticide fate and effects, and to determine whether in-stream nitrate concentration was a useful surrogate indicator for regional monitoring of toxic substances. Significant correlations were observed between pesticide application rates and in-stream pesticide concentrations (p < 0.05) and toxicity (p < 0.10). In-stream nitrate concentrations were not significantly correlated with either the amount of pesticides applied, in-stream pesticide concentrations, or in-stream toxicity (all p > 0.30). Neither total watershed area nor the area in which pesticide usage was reported correlated significantly with the amount of pesticides applied, in-stream pesticide concentrations, or in-stream toxicity (all p > 0.14). In-stream pesticide concentrations and effects were more closely related to the intensity of pesticide use than to the area under cultivation.     

Stormwater toxicity in Chollas Creek and San Diego Bay,California

Stormwater discharges from Chollas Creek, a tributary of San Diego Bay, have been shown to be toxic to aquatic life. The primary objective of this study was to provide the linkage between in-channel measurements and potential impairments in the receiving waters of San Diego Bay. This study addressed this objective within the context of four questions: (1) How much area in San Diego Bay is affected by the discharge plume from Chollas Creek during wet-weather conditions?; (2) How much of the wet-weather discharge plume is toxic to marine aquatic life?; (3) How toxic is this area within the wet-weather discharge plume?; and (4) What are the constituent(s) responsible for the observed toxicity in the wet-weather plume? The stormwater plume emanating from Chollas Creek was dynamic, covering areas up to 2.25 km2. Approximately half of the plume was estimated to be toxic to marine life, based upon the results of purple sea urchin (Strongylocentroutus purpuratus) fertilization tests. The area nearest the creek mouth was the most toxic (NOEC = 3 to 12% plume sample), and the toxicity decreased with distance from the creek mouth. The toxicity of plume samples was directly proportional to the magnitude of plume mixing and dilution until, once outside the plume margin, no toxicity was observed. Trace metals, most likely zinc, were responsible for the observed plume toxicity based upon toxicity identification evaluations (TIEs). Zinc was also the constituent identified from in-channel samples of Chollas Creek stormwater using TIEs on the storms sampled in this study, and in storms sampled during the previous storm season.     

Effects of Acid Rock Drainage on Stocked Rainbow Trout (Oncorhynchus mykiss): An In-Situ, Caged Fish Experiment

In-situ caged rainbow trout (Oncorhynchus mykiss) studies reveal significant fish toxicity and fish stress in a river impacted by headwater acid rock drainage (ARD). Stocked trout survival and aqueous water chemistry were monitored for 10 days at 3 study sites in the Snake River watershed, Colorado, U.S.A. Trout mortality was positively correlated with concentrations of metals calculated to be approaching or exceeding conservative toxicity thresholds (Zn, Mn, Cu, Cd). Significant metal accumulation on the gills of fish stocked at ARD impacted study sites support an association between elevated metals and fish mortality. Observations of feeding behavior and significant differences in fish relative weights between study site and feeding treatment indicate feeding and metals-related fish stress. Together, these results demonstrate the utility of in-situ exposure studies for stream stakeholders in quantifying the relative role of aqueous contaminant exposures in limiting stocked fish survival.     

Phosphate run-off in the Nevezis River (Lithuania)

The long-term (40 yr) observation results of phosphates–phosphorus concentration and its runoff in the Lithuanian fourth largest river Nevezis are analysed. Amounts and peculiarities of background runoff, agricultural runoff, andpoint source pollution from towns were studied for various periods. It has been determined that phosphates enter into the river Nevezis mainly from towns (76.5%), from agricultureonly up to 16%, and the background runoff for 7.5%.Considerable agricultural influence was observed in 1979–1991,when the phosphate runoff increased to 22 kg P km^-2 a^-1 and formed in 1984 33% of the entire runoff. A relation of the phosphates runoff from agriculture, for the entire study period, was obtained with the number of animals in the river's basin. Since 1990, when the number of animals started to decrease, the runoff of phosphates decreased too. Now the phosphatesrunoff from agriculture formed only 2% of the entire runoff. Water in the river Nevezis is heavily polluted with phosphate,according to the EU general classification of the water quality of rivers, although the Lithuanian pollution norms for effluentsdischarging to surface water are not exceeded. Norms for effluents discharging in the rivers from point-sources pollution should be made stricter and the highest permitted ratiobetween the phosphorus load in the river and its waterdischarge should be established.     

平原感潮河网地区农业非点源污染产污规律

平原感潮河网地区非点源污染严重,同时由于本身具有的交叉污染等特性,造成了整个平原河网存在严重的环境污染和环境安全问题。文章在南通平原河网地区选择圩区作为典型区,以野外观测和室内分析相结合的方法开展野外原位试验,研究平原河网典型圩区各形态污染物随降雨径流的迁移特征,建立了稻季农田营养盐的迁移通量与径流通量、施肥量及降雨距施肥时间间隔三者之间的定量化关系。     

Nonpoint Source Pollution Assessment of Wujiang RiverWatershed in Guizhou Province,SW China

The amount of pollution from nonpoint sources flowing in the streams of the Wujiang River watershed in Guizhou Province, SW China, is estimated by a geographic information system (GIS)-based method using rainfall, surface runoff and land use data. A grid of cells of 100 m in size is laid over the landscape. For each cell, mean annual surface runoff is estimated from rainfall and percent land use, and expected pollutant concentration is estimated from land use. The product of surface runoff and concentration gives expected pollutant loading from that cell. These loadings are accumulated going downstream to give the expected annual pollutant loadings in streams and rivers. By dividing these accumulated loadings by the similarly accumulated mean annual surface runoff, the expected pollutant concentration from nonpoint sources is determined for each location in a stream or river. Observed pollutant concentrations in the watershed are averaged at each sample point and compared to the expected concentrations at the same locations determined from the grid cell model. In general, annual nonpoint source nutrient loadings in the Wujiang River watershed are seen to be predominantly from the agricultural and meadow areas. The total annual loadings through the outlet of the watershed are 40,309 and 2,607 tons for total nitrogen (TN) and total phosphorus (TP), respectively.     

An interlaboratory comparison of sediment elutriate preparation and toxicity test methods

Elutriate bioassays are among numerous methods that exist for assessing the potential toxicity of sediments in aquatic systems. In this study, interlaboratory results were compared from 96-h Ceriodaphnia dubia and Pimephales promelas static-renewal acute toxicity tests conducted independently by two laboratories using elutriate samples prepared from the same sediment. The goal of the study was to determine if the results from the elutriate tests were comparable between two U.S. Environmental Protection Agency (USEPA) laboratories when different elutriate preparation procedures were employed by each lab. Complete agreement in site characterization was attained in 22 of the 25 samples for both bioassays amongst each lab. Of the 25 samples analyzed, 10 were found to be toxic to at least one of the species tested by either laboratory. The C. dubia elutriate tests conducted by the National Exposure Research Laboratory (NERL) indicated that 7 of the 25 sediment samples were toxic, while 8 sediment samples were characterized as such in testing conducted by USEPA Region 6 (Region 6). The P. promelas elutriate tests conducted by NERL determined 8 samples as toxic, while Region 6 tests displayed toxicity in 5 of the samples. McNemar's test of symmetry for C. dubia (S?=?0.33, p?=?0.5637) and P. promelas (S?=?3.0, p?=?0.0833) tests indicated no significant differences in designating a site toxic between NERL and Region 6 laboratories. Likewise, Cohen's kappa test revealed significant agreement between NERL and Region 6 C. dubia (K?=?0.7148, p?<?0.01) and P. promelas (K?=?0.6939, p?<?0.01) elutriate tests. The authors conclude that differences in interlaboratory elutriate preparation procedures have no bearing on the ability of either the C. dubia or P. promelas bioassay testing methods to detect toxicity while yielding similar results.     

Community air monitoring for pesticides. Part 3: using health-based screening levels to evaluate results collected for a year

The CA Department of Pesticide Regulation (CDPR) and the CA Air Resources Board monitored 40 pesticides, including five degradation products, in Parlier, CA, to determine if its residents were exposed to any of these pesticides and, if so, in what amounts. They included 1,3-dichloropropene, acrolein, arsenic, azinphos-methyl, carbon disulfide, chlorpyrifos and its degradation product, chlorthalonil, copper, cypermethrin, diazinon and its degradation product, dichlorvos, dicofol, dimethoate and its degradation product, diuron, endosulfan and its degradation product, S-ethyl dipropylcarbamothioate (EPTC), formaldehyde, malathion and its degradation product, methyl isothiocyanate (MITC), methyl bromide, metolachlor, molinate, norflurazon, oryzalin, oxyfluorfen, permethrin, phosmet, propanil, propargite, simazine, SSS-tributylphosphorotrithioate, sulfur, thiobencarb, trifluralin, and xylene. Monitoring was conducted 3 days per week for a year. Twenty-three pesticides and degradation products were detected. Acrolein, arsenic, carbon disulfide, chlorpyrifos, copper, formaldehyde, methyl bromide, MITC, and sulfur were detected in more than half the samples. Since no regulatory ambient air standards exist for these pesticides, CDPR developed advisory, health-based non-cancer screening levels (SLs) to assess acute, subchronic, and chronic exposures. For carcinogenic pesticides, CDPR assessed risk using cancer potency values. Amongst non-carcinogenic agricultural use pesticides, only diazinon exceeded its SL. For carcinogens, 1,3-dichloropropene concentrations exceeded its cancer potency value. Based on these findings, CDPR has undertaken a more comprehensive evaluation of 1,3-dichloropropene, diazinon, and the closely related chlorpyrifos that was frequently detected. Four chemicals—acrolein, arsenic, carbon disulfide, and formaldehyde—sometimes used as pesticides were detected, although no pesticidal use was reported in the area during this study. Their presence was most likely due to vehicular or industrial emissions.     

Occurrence and distribution of benzothiazole in the Schwarzbach watershed (Germany)

This study quantifies the regional distribution of the micropollutant benzothiazole (BT) in river water by sampling 15 river sites in the Schwarzbach watershed (about 400 km(2)) from November 2008 to February 2010. Additionally, wastewater samples from three municipal wastewater treatment plants (WWTPs) in Germany were analyzed. BT was detected in all wastewater influent and effluent samples as well as in all river water samples collected downstream of wastewater discharge. This corroborates the ubiquitous occurrence of BT in the aqueous environment. Concentrations were between 58 and 856 ng L(-1) in the river water. The observed mean concentration at the outlet of the investigated catchment was 109 ng L(-1). With only a few exceptions, temporal and spatial variations of BT concentrations in river water were low. Rather similar BT concentrations over a wide range of river discharge indicate that dilution along the mainstream is negligible and, thus, supports the hypothesis that paved surface runoff during rain events is an important BT source not only for wastewater influent but also for river water. This was supported by detecting the highest BT concentrations at sampling locations close to the dense highway network around the city of Frankfurt. Since BT was also detected in river water collected from locations that were clearly unaffected by wastewater effluent discharge, surface runoff must be considered as a diffuse source of BT in river water.     

Integrated approach for the quality assessment of freshwater resources in a vineyard area (South Portugal)

An integrated chemical and biological approach for the quality assessment of freshwater resources in a vineyard area of the ??Alentejo?? region (South Portugal) is presented. This includes analysis to 11 pesticide compounds and whole toxicity testing on algae and crustaceans. Simazine, terbuthylazine, terbutryn, desethylatrazine and chlorpyrifos were the most frequently detected pesticides in water collected from wells and drainage channels. Mixtures of up to three compounds in different qualitative combinations were also found. The quality standards for individual pesticides (0.1 ??g L^???1) and pesticides-total (0.5 ??g L^???1) were exceeded in some samples. However, their maximum concentrations were lower than the WHO guidelines, the USEPA health advisory values and the environmental quality standards for priority substances applicable to surface water. In five samples, the herbicides terbuthylazine and terbutryn and the insecticide chlorpyrifos did not pass the toxicity exposure ratio (TER) trigger values specified for aquatic organisms (algae, Daphnia and fish). Maximum toxic effects on Daphnia magna (100%) and Pseudokirchneriella subcapitata (82.56%) were determined in groundwater samples, while in surface water, no toxicity was observed. Concerning effects on Heterocypris incongruens in sediment samples collected at the drainage channels, mortality and growth inhibition values were below 38%. Pro-active management of the use of pesticides is recommended for implementing at the farm and catchment level to reduce inputs into ground- and surface water.     

Whole Effluent Toxicity (WET) Tests on Wastewater Treatment Plants with Daphnia magna and Selenastrum capricornutum

Whole effluent toxicity (WET) tests, with Daphnia magna and Selenastrum capricornutum, were introduced to evaluate the biological toxicities of effluents from the wastewater treatment plants (WWTPs) in Korea. In WET tests of WWTPs effluents, 33.3% (33/99) for D. magna and 92.6% (75/81) for S. capricornutum revealed greater than 1 toxic unit (TU), even though all the treatment plants investigated were operating in compliance with the regulations, as assessed using conventional monitoring methods (i.e., BOD and total concentration of N or P, etc). There were only minor differences in toxicities according to the types of influents (municipal and agro-industrial) in all treatment plants. However, the effluents treated by an activated sludge treatment process were found to exhibit significantly lower toxicity than those treated by rotating biological contactor (RBC) and extended aeration processes. The seasonal variations in the toxicity were lower in the summer compared to winter, which may have been due to the rainfall received to the sewage intake system during the former period. The impact of WET on river water was also investigated based on the discharge volume. At sites A and B, the total impact of toxicity to stream and river waters was observed to be 70.9% and 90.4% for D. magna and S. capricornutum, respectively. The other four small treatment plants (sites F, G, H and I), with relative discharging volumes between 0.001 and 0.002, contribute less than 1% to the total toxicity.     

Chemometric application in identifying sources of organic contaminants in Langat river basin

Increasing urbanization and changes in land use in Langat river basin lead to adverse impacts on the environment compartment. One of the major challenges is in identifying sources of organic contaminants. This study presented the application of selected chemometric techniques: cluster analysis (CA), discriminant analysis (DA), and principal component analysis (PCA) to classify the pollution sources in Langat river basin based on the analysis of water and sediment samples collected from 24 stations, monitored for 14 organic contaminants from polycyclic aromatic hydrocarbons (PAHs), sterols, and pesticides groups. The CA and DA enabled to group 24 monitoring sites into three groups of pollution source (industry and urban socioeconomic, agricultural activity, and urban/domestic sewage) with five major discriminating variables: naphthalene, pyrene, benzo[a]pyrene, coprostanol, and cholesterol. PCA analysis, applied to water data sets, resulted in four latent factors explaining 79.0% of the total variance while sediment samples gave five latent factors with 77.6% explained variance. The varifactors (VFs) obtained from PCA indicated that sterols (coprostanol, cholesterol, stigmasterol, β-sitosterol, and stigmastanol) are strongly correlated to domestic and urban sewage, PAHs (naphthalene, acenaphthene, pyrene, benzo[a]anthracene, and benzo[a]pyrene) from industrial and urban activities and chlorpyrifos correlated to samples nearby agricultural sites. The results demonstrated that chemometric techniques can be used for rapid assessment of water and sediment contaminations.     

平原感潮河网地区不同土地利用下营养盐迁移特征

分别在南通平原河网地区选择典型非圩区开展野外原位试验,用野外观测和室内分析相结合的方法,研究平原非圩区典型试验小区不同土地利用下营养盐在自然降雨—径流驱动下迁移的时空分布特征.结果表明,导致营养盐迁移时空分布存在显著差异的主要原因为不同的土地利用类型、施肥条件及植被覆盖度等,不同土地利用下的径流量差异是导致营养盐迁移通...     

Physicochemical factors affecting the sensitivity of Ceriodaphnia dubia to copper

The effects of physicochemical conditions, such as pH, water hardness, flow rates and natural organic substances on the sensitivity of Ceriodaphnia dubia to the toxic effects of copper were investigated using static bioassay cups and specially designed flow-through bioassay chambers. We found that C.dubia was very sensitive to pH changes and the total copper LC50 values of C. dubia neonates increased by 15-fold as the pH increased from pH 7 to 10. It was also observed that the LC50 values increased sharply upon increasing the water hardness value to 2.4 meq. In addition, increasing flow rates from zeroto 50 mL hr^-1 also increased its sensitivity to copper, which was possibly due to hydrodynamic stress.The presence of natural organic substances (humic acid and dissolved organic matter) and suspended particles decreased thetoxic effect of copper. This significant decrease in the toxicity of copper in the presence of natural organic materialscan be explained by a reduction in the free ion concentration due to complexation. Furthermore, we observed that the kinetics of copper interactions with natural organic materials are a significant factor in the toxic effect of copper and that the acute LC50 values increased with increasing reaction time betweensolubilized copper and water-borne organics.