Gary M. Rand

A review of personal care products in the aquatic environment: environmental concentrations and toxicity.

Considerable research has been conducted examining occurrence and effects of human use pharmaceuticals in the aquatic environment; however, relatively little research has been conducted examining personal care products although they are found more often and in higher concentrations than pharmaceuticals. Personal care products are continually released into the aquatic environment and are biologically active and persistent. This article examines the acute and chronic toxicity data available for personal care products and highlights areas of concern. Toxicity and environmental data were synergized to develop a preliminary hazard assessment in which only triclosan and triclocarban presented any hazard. However, numerous PCPs including triclosan, paraben preservatives, and UV filters have evidence suggesting endocrine effects in aquatic organisms and thus need to be investigated and incorporated in definitive risk assessments. Additional data pertaining to environmental concentrations of UV filters and parabens, in vivo toxicity data for parabens, and potential for bioaccumulation of PCPs needs to obtained to develop definitive aquatic risk assessments.

Pesticides of Potential Ecological Concern in Sediment from South Florida Canals: An Ecological Risk Prioritization for Aquatic Arthropods

A two-tier ecological risk assessment was conducted for pesticides monitored in sediment at 36 sampling sites in south Florida freshwater canals from 1990–2002. For tier 1, we identified the chemicals of potential ecological concern (COPECs) as DDT, DDD, DDE, chlordane and endosulfan based on their exceedence of sediment quality standards at 20 sites. For 12 sites with data on the fraction of organic carbon in sediments, whole sediment concentrations of COPECs were converted to pore water concentrations based on equilibrium partitioning. In tier 2, a probabilistic risk assessment compared distributions of pore water exposure concentrations of COPECs with effects distributions of freshwater arthropod response data from laboratory toxicity tests. Arthropod effects distributions included benthic and non-benthic arthropod species for chlordane (n = 9), DDD (n = 12), DDE (n = 5), DDT (n = 48), and endosulfan (n = 26). The overlap of predicted pore water concentrations and arthropod effects distributions was used as a measure of risk. DDE was the most frequently detected COPEC in sediment at the 12 sites. Chlordane was present at only one site. The mean 90th centile concentration for pore water exposure was highest for endosulfan and lowest for DDT. The estimated acute 10th centile concentration for effects was highest for chlordane and lowest for DDD. The probability of pore water exposures of COPECs exceeding the estimated 10th centile concentrations for species sensitivity distributions of arthropod acute toxicity data was between 0 and 1%. The estimated NOEC 10th centile concentration from arthropod chronic toxicity distributions was exceeded by the estimated 90th centile concentration for pore water distributions at three sites. Endosulfan had the highest potential chronic risk at S-178 in the C-111 canal system, based on the probability of pore water exposure concentrations exceeding the arthropod estimated chronic NOEC 10th centile at 41%. The COPEC with the next highest probability of exceeding the chronic NOEC 10th centile was DDD at 17.7% and 19.8% in the Everglades Agricultural Area (at S-2 and S-6). DDT had minimal potential chronic risk. Uncertainties in exposure and effects analysis and risk characterization are discussed.

Endosulfan and its metabolite, endosulfan sulfate, in freshwater ecosystems of South Florida: a probabilistic aquatic ecological risk assessment

Endosulfan is an insecticide–acaricide used in South Florida and is one of the remaining organochlorine insecticides registered under the Federal Insecticide Fungicide and Rodenticide Act by the U.S.EPA. The technical grade material consists of two isomers (α-, β-) and the main environmental metabolite in water, sediment and tissue is endosulfan sulfate through oxidation. A comprehensive probabilistic aquatic ecological risk assessment was conducted to determine the potential risks of existing exposures to endosulfan and endosulfan sulfate in freshwaters of South Florida based on historical data (1992–2007). The assessment included hazard assessment (Tier 1) followed by probabilistic risk assessment (Tier 2). Tier 1 compared actual measured concentrations in surface freshwaters of 47 sites in South Florida from historical data to U.S.EPA numerical water quality criteria. Based on results of Tier 1, Tier 2 focused on the acute and chronic risks of endosulfan at nine sites by comparing distributions of surface water exposure concentrations of endosulfan [i.e., for total endosulfan (summation of concentrations of α- and β-isomers plus the sulfate), α- plus β-endosulfan, and endosulfan sulfate (alone)] with distributions of species effects from laboratory toxicity data. In Tier 2 the distribution of total endosulfan in fish tissue (whole body) from South Florida freshwaters was also used to determine the probability of exceeding a distribution of whole body residues of endosulfan producing mortality (critical lethal residues). Tier 1 showed the majority of endosulfan water quality violations in South Florida were at locations S-178 followed by S-177 in the C-111 system (southeastern boundary of Everglades National Park (ENP)). Nine surface water sampling sites were chosen for Tier 2. Tier 2 showed the highest potentially affected fraction of toxicity values (>10%) by the estimated 90th centile exposure concentration (total endosulfan) was at S-178. At all other freshwater sites there were <5% of the toxicity values exceeded. Potential chronic risk (9.2% for total endosulfan) was only found at S-178 and all other sites were <5%. Joint probability curves showed the higher probability of risk at S-178 than at S-177. The freshwater fish species which contain tissue concentrations of endosulfan (total) with the highest potential risk for lethal whole body tissue residues were marsh killifish, flagfish and mosquitofish. Based on existing surface water exposures and available aquatic toxicity data, there are potential risks of total endosulfan to freshwater organisms in South Florida. Although there are uncertainties, the presence of tissue concentrations of endosulfan in small demersal fish, is of ecological significance since these fish support higher trophic level species, such as wading birds.

South Florida Ambient Pesticide Monitoring Program

The South Florida Water Management District is a state agency that manages surface and ground water quantity and quality in south Florida. Since 1984 surface water and sediment have been sampled for pesticides at various frequencies and locations in the Districts 1400-mile system of canals. Based on monitoring data from 1992 to 2001 the most common pesticides detected in surface water samples were herbicide compounds, especially ametryn and atrazine, while DDE and DDD were the most frequently detected in sediment samples. Exceedances of state surface water quality standards occurred in certain basins for several insecticides including endosulfan. In addition, the concentrations of several ubiquitous organochlorine compounds in sediment were similar to or exceeded threshold effect levels based on a comparison to the NOAA screening quick reference tables (or SQuiRTs) for sediment.

Aquatic risk assessment of pesticides in surface waters in and adjacent to the Everglades and Biscayne National Parks: I. Hazard assessment and problem formulation

An aquatic risk assessment under the U.S. Environment Protection Agency (EPA) ecological risk framework was conducted for atrazine, metolachlor, malathion, chlorpyrifos, and endosulfan in the C-111 freshwater basin (eastern boundary of the Everglades National Park), northeast Florida Bay, and south Biscayne Bay in South Florida. Based on the use of the hazard quotient approach, measured concentrations of chlorpyrifos and endosulfan in surface waters suggest potential hazards to aquatic organisms and were, therefore, considered as chemicals of potential ecological concern (COPECs). The problem formulation included an overview of the physical/chemical and environmental fate characteristics and aquatic toxicology of the COPECs. Background surface water exposure concentrations of endosulfan and toxicity data from laboratory and field studies indicate that fish and invertebrate mortality may be a concern when endosulfan is applied in agricultural areas near aquatic ecosystems.

The Effects of Water Quality and Age on the Acute Toxicity of Copper to the Florida Apple Snail, Pomacea paludosa

Copper (Cu)-containing compounds have been used in Florida as fungicides, herbicides, and soil amendments, resulting in elevated Cu in the aquatic ecosystem. The Florida apple snail (Pomacea paludosa), a key species in south Florida, may be adversely affected by Cu. Water-quality parameters, such as hardness, dissolved organic carbon (DOC), pH, and alkalinity, affect metal bioavailability and toxicity in aquatic organisms; however, it is uncertain to what extent these factors affect Cu toxicity in the Florida apple snail. The research presented here characterized the acute (96-hour) toxicity of Cu in water to the Florida apple snail at various life stages and under different water-quality parameters. Cu was more toxic to juvenile than adult apple snails. There was no difference between the 96-hour LC50 at pH 5.5 and 6.5; however, the 96-hour LC50 values at pH 7.5 and 8.5 were greater than at lower pHs. The decrease in Cu2+ above pH 7, as predicted by the MINTEQ model, accounted for the pH effect. Cu toxicity decreased as DOC increased from 0.2 to 30 mg/L. Unlike other aquatic organisms, hardness had no effect on Cu toxicity to the Florida apple snail, suggesting another mechanism of toxicity. Whole-body tissue analysis indicated that the lethal body burden of 120-day-old snails exposed to Cu for 4 days was 30 mg/kg Cu dry weight. Multiple regression analysis indicated that Cu toxicity was a function of organism age, DOC, and pH.

Copper uptake and depuration by juvenile and adult Florida apple snails (Pomacea paludosa)

The present study characterized copper (Cu) uptake and depuration by juvenile and adult Florida apple snails (Pomacea paludosa) from water, soil, and diet. During a 28-day uptake period, juvenile apple snails were exposed to aqueous Cu and adult apple snails were exposed to Cu-contaminated soil, water, and food. In the follow-up 14-day depuration period, both juvenile and adult apple snails were held in laboratory freshwater with background Cu concentrations <4 μg/l. For juvenile apple snails, whole body Cu concentrations increased with time and reached a plateau after 14 days. The data followed Michaelis–Menten kinetics rather than a one compartment first order kinetics model. The mean Cu bioconcentration factor (BCF) for juvenile apple snails was 1493 and the depuration half-life was 10.5–13.8 days. For adult snails, dietary uptake of Cu resulted in higher bioaccumulation factors (BAFs) compared to uptake from soil. Most of the accumulated Cu was located in soft tissue (about 60% in the viscera and 40% in the foot). The shell contained <1% of the total accumulated copper. Soft tissue is usually consumed by predators of the apple snail. Therefore, the results of the present study show that Cu transfer through the food chain to the apple snail may lead to potential risk to its predators.

Use of butterflies as nontarget insect test species and the acute toxicity and hazard of mosquito control insecticides

Honeybees are the standard insect test species used for toxicity testing of pesticides on nontarget insects for the U.S. Environmental Protection Agency (U.S. EPA) under the Federal Insecticide Fungicide and Rodenticide Act (FIFRA). Butterflies are another important insect order and a valued ecological resource in pollination. The current study conducted acute toxicity tests with naled, permethrin, and dichlorvos on fifth larval instar (caterpillars) and adults of different native Florida, USA, butterfly species to determine median lethal doses (24-h LD50), because limited acute toxicity data are available with this major insect group. Thorax- and wing-only applications of each insecticide were conducted. Based on LD50s, thorax and wing application exposures were acutely toxic to both caterpillars and adults. Permethrin was the most acutely toxic insecticide after thorax exposure to fifth instars and adult butterflies. However, no generalization on acute toxicity (sensitivity) of the insecticides could be concluded based on exposures to fifth instars versus adult butterflies or on thorax versus wing exposures of adult butterflies. A comparison of LD50s of the butterflies from this study (caterpillars and adults) with honeybee LD50s for the adult mosquito insecticides on a µg/organism or µg/g basis indicates that several butterfly species are more sensitive to these insecticides than are honeybees. A comparison of species sensitivity distributions for all three insecticides shows that permethrin had the lowest 10th percentile. Using a hazard quotient approach indicates that both permethrin and naled applications in the field may present potential acute hazards to butterflies, whereas no acute hazard of dichlorvos is apparent in butterflies. Butterflies should be considered as potential test organisms when nontarget insect testing of pesticides is suggested under FIFRA.

Exposure routes of copper: Short term effects on survival, weight, and uptake in Florida apple snails (Pomacea paludosa)

The uptake and effects (survival, weight) of copper (Cu) on Florida apple snails (Pomacea paludosa) via exposures to copper-enriched agricultural soil-water and water-only treatments were investigated. Soils were collected from citrus sites in south Florida and flooded with laboratory freshwater for 14d. Neonate apple snails (96-h-old) were then exposed to either Cu from a soil-overlying water (i.e., flooded agricultural soils) treatment or overlying water-only (i.e., equilibrated overlying water produced from 14d flooding of agriculture soils) treatment for 14d under standard laboratory conditions. Survival, weight (dry, wet), and whole body Cu uptake were measured. Copper exposure via soil-water exposures resulted in higher mortality and whole body Cu uptake than water-only exposures, indicating Cu uptake from soils. However, snail wet and dry weights were higher in soil-water treatments than in water-only treatments. Micronutrients from soils may be consumed by snails increasing weights. Survival, apple snail dry weight, and whole body Cu concentrations were significantly correlated with soil and water Cu concentrations in soil-water treatments. Survival was significantly correlated with the concentration of Cu(CO3)2(2-) in water-only treatments. This suggests that Cu(CO3)2(2-) is toxic to apple snails. Whole body Cu concentrations were higher in surviving snails than dead snails, suggesting that apple snails have the ability to detoxify accumulated Cu (e.g., through metallothionein induction, granules).

Aquatic risk assessment of pesticides in surface waters in and adjacent to the Everglades and Biscayne National Parks: II. Probabilistic analyses.

A screening-level aquatic probabilistic risk assessment was completed to determine the potential risks of organic pesticides found in surface waters of the C-111 freshwater basin (11 sites at the east boundary of the Everglades National Park) and adjacent estuarine tidal zones (two sites in northeast Florida Bay, one site in south Biscayne Bay) in south Florida. It followed the US Environmental Protection Agency (USEPA) ecological risk framework and focused only on the acute and chronic risks of endosulfan and chlorpyrifos individually and jointly with atrazine, metolachlor, and malathion by comparing distributions of surface water exposure concentrations with the distributions of species toxicity data. The highest risk of acute effects was associated with endosulfan exposure to freshwater arthropods at S-178/site C on the C-111 system, followed by endosulfan effects to estuarine arthropods at Joe Bay in northeast Florida Bay. The highest risk of acute effects from joint toxicity of pesticides was to estuarine arthropods in Joe Bay followed by freshwater arthropods in S-178/site C. For fish, the highest acute risk was for endosulfan at S-178/site C. There was low potential for acute risk of endosulfan to fish at estuarine sites. Joint probability curves indicated that the majority of potential risks to arthropods and fish were due to endosulfan concentrations and not to chlorpyrifos, at S-178/site C. In addition, the highest risk of acute effects for saltwater organisms was in Joe Bay, which receives water from the C-111. The potential risk of chronic effects from pesticide exposures was minimal at fresh- and saltwater sites except at S-178/site C, where endosulfan concentrations showed the highest exceedence of species toxicity values. In general, potential risks were higher in February than June.