Environmental dynamics of phosphate esters. III. Comparison of the bioconcentration of four triaryl phosphates by fish

Uptake, clearance and extent of metabolism of ¹⁴C-labelled t-butylphenyldiphenyl phosphate (t-BPDP), tri-m-cresyl phosphate (mTCP), tri-p-cresyl phosphate (pTCP) and triphenyl phosphate (TPP) were studied in rainbow trout ($\text{Salmo}$$\text{gairdneri}$) and fathead minnows ($\text{Pimephales}$$\text{promelas}$) using short-term static exposures (50 and 5 μmg/L). Bioconcentration factors for pTCP, mTCP, TPP and tBPDP calculated by use of total radioactivity in whole fish were 1420, 784, 573 and 1096 respectively, for rainbow trout and 928, 596, 561 and 1010 respectively, for fathead minnows. Differences in rates of clearance and biotransformation among the four compounds were more closely related to their ease of hydrolysis than to hydrophobicity.     

Water quality status and trends in agriculture-dominated headwaters; a national monitoring network for assessing the effectiveness of national and European manure legislation in The Netherlands

Large nutrient losses to groundwater and surface waters are a major drawback of the highly productive agricultural sector in The Netherlands. The resulting high nutrient concentrations in water resources threaten their ecological, industrial, and recreational functions. To mitigate eutrophication problems, legislation on nutrient application in agriculture was enforced in 1986 in The Netherlands. The objective of this study was to evaluate this manure policy by assessing the water quality status and trends in agriculture-dominated headwaters. We used datasets from 5 agricultural test catchments and from 167 existing monitoring locations in agricultural headwaters. Trend analysis for these locations showed a fast reduction of nutrient concentrations after the enforcement of the manure legislation (median slopes of ?0.55 mg/l per decade for total nitrogen (N-tot) and ?0.020 mg/l per decade for total phosphorus (P-tot)). Still, up to 76 % of the selected locations currently do not comply with either the environmental quality standards (EQSs) for nitrogen (N-tot) or phosphorus (P-tot). This indicates that further improvement of agricultural water quality is needed. We observed that weather-related variations in nutrient concentrations strongly influence the compliance testing results, both for individual locations and for the aggregated results at the national scale. Another important finding is that testing compliance for nutrients based on summer average concentrations may underestimate the agricultural impact on ecosystem health. The focus on summer concentrations does not account for the environmental impact of high winter loads from agricultural headwaters towards downstream water bodies.     

Environmental dynamics of phosphate esters. II. Uptake and bioaccumulation of 2-ethylhexyl diphenyl phosphate and diphenyl phosphate by fish

Uptake, clearance and disposition of ¹⁴C-labelled 2-ethylhexyl diphenyl phosphate (EHDP) and ¹⁴C-diphenyl phosphate (DPP) by rainbow trout (Salmo gairdneri) were investigated using short-term static exposures. Bioconcentration factors of 1314 and 0.3 were calculated for EHDP and DPP, respectively. Highest levels of radioactivity were found in liver and intestine following exposure to 60 μg/L EHDP. A portion (up to 40%) of the radioactivity in each tissue was in the form of DPP while a similar portion was extractable with methanol but could not be identified.     

Herbicide levels in rivers draining two prairie agricultural watersheds (1984)

A monitoring survey was conducted during 1984 on the Ochre and Turtle Rivers, which flow into Dauphin Lake in western Manitoba, Canada, to determine levels of the herbicides MCPA, diclofop-methyl, dicamba, bromoxynil, 2,4-D, triallate and trifluralin which were widely used in each watershed. Triallate concentrations exceeded 4 ng/L in 50% and 10% of the 21 samples taken from each of the Turtle and Ochre River, respectively, during the period March to October 1984. Trifluralin concentrations exceeded 3 ng/L in 14% and 10% of the samples from the respective rivers. Maximum concentrations did not exceed 25 ng/L and were unrelated to changes in river flow. Bromoxynil and diclofop were detected in the Turtle River, at concentrations of 113 and 476 ng/L, respectively, following a major high water event in late June, but were undetectable (less than 2 and 12 ng/L, respectively) at other sampling times. Dicamba and 2,4-D were detectable throughout most of the sampling period in both rivers at low levels (less than 100 ng/L). High levels of dicamba and 2,4-D (5476 and 2568 ng/L respectively) were found in water from the Turtle River prior to the high water event event possibly caused by spraying of ditches or rights-of-way near the river. Discharges (grams/year) of all seven herbicides monitored in the study represented less than 0.1% of the amounts estimated to be used in each watershed. Unit loadings (mg/ha/year) of 2,4-D and dicamba were similar to those reported for Southern Ontario streams in the mid-1970's. The results indicate that herbicide contamination of Manitoba streams draining agricultural areas is generally low except when major runoff occurs during the application period in May and June.     

Modelling assessment of regional groundwater contamination due to historic smelter emissions of heavy metals

Historic emissions from ore smelters typically cause regional soil contamination. We developed a modelling approach to assess the impact of such contamination on groundwater and surface water load, coupling unsaturated zone leaching modelling with 3D groundwater transport modelling. Both historic and predictive modelling were performed, using a mass balance approach for three different catchments in the vicinity of three smelters. The catchments differ in their hydrology and geochemistry. The historic modelling results indicate that leaching to groundwater is spatially very heterogeneous due to variation in soil characteristics, in particular soil pH. In the saturated zone, cadmium is becoming strongly retarded due to strong sorption at neutral pH, even though the reactivity of the sandy sediments is low. A comparison between two datasets (from 1990 to 2002) on shallow groundwater and modelled concentrations provided a useful verification on the level of statistics of "homogeneous areas" (areas with comparable land use, soil type and geohydrological situation) instead of comparison at individual locations. While at individual locations observations and the model varies up to two orders of magnitude, for homogeneous areas, medians and ranges of measured concentrations and the model results are similar. A sensitivity analysis on metal input loads, groundwater composition and sediment geochemistry reveals that the best available information scenario based on the median value of input parameters for the model predicts the range in observed concentrations very well. However, the model results are sensitive to the sediment contents of the reactive components (organic matter, clay minerals and iron oxides). Uncertainty in metal input loads and groundwater chemistry are of lesser importance. Predictive modelling reveals a remarkable difference in geochemical and hydrological controls on subsurface metal transport at catchment-scale. Whether the surface water load will peak within a few decades or continue to increase until after 2050 depends on the dominant land use functions in the areas, their hydrology and geochemical build-up.     

Demonstrating trend reversal of groundwater quality in relation to time of recharge determined by 3H/3He

Recent EU legislation is directed to reverse the upward trends in the concentrations of agricultural pollutants in groundwater. However, uncertainty of the groundwater travel time towards the screens of the groundwater quality monitoring networks complicates the demonstration of trend reversal. We investigated whether trend reversal can be demonstrated by relating concentrations of pollutants in groundwater to the time of recharge, instead of the time of sampling. To do so, we used the travel time to monitoring screens in sandy agricultural areas in the Netherlands, determined by (3)H/(3)He groundwater dating. We observed that concentrations of conservative pollutants increased in groundwater recharged before 1985 and decreased after 1990. Thereby, we demonstrated trend reversal of groundwater quality. From this research we concluded that (3)H/(3)He dating can be used to facilitate (re)interpretation of existing groundwater quality data. The presented approach is widely applicable in areas with unconsolidated granular aquifers and large agricultural pressures on groundwater resources.     

Development of a regional hydrologic soil model and application to the Beerze--Reusel drainage basin

The soil compartment is an important interface between the atmosphere and the subsurface hydrosphere. In this paper a conceptual approach for regional hydrologic soil modelling (RHSM) is presented, which provides two important qualities for modelling. First, the soil compartment is directly coupled to the atmosphere via the land surface and to the aquifers. Second, extremely fine (5cm vertical) resolutions of the soil system can be realized at regional scales (several hundreds of km(2)). This high-resolution modelling could be achieved by parallel computation techniques. The RHSM approach is applied to the Beerze-Reusel drainage basin, which belongs to the Meuse River basin. Moisture transport in the soil system was calculated with extremely high vertical resolution at a regional scale based on rainfall-evaporation data for the year 2000. As a result, highly resolved regional groundwater recharge pattern addressing the heterogeneity of soil systems could be determined.     

Organochlorine contaminants in narwhal (Monodon monoceros) from the Canadian Arctic

Organochlorine pesticides (DDT, chlordane, polychlorinated camphenes (PCCs), dieldrin, hexachloroheclohexanes (SigmaHCH), mirex), polychlorinated biphenyl congeners (PCBs) and chlorobenzenes (SigmaCBz) were determined in blubber and liver of narwhal (Monodon monoceros) collected during 1982-1983 from Pond Inlet on northern Baffin Island in the Canadian Arctic. PCCs were the predominate organochlorines in narwhal blubber, ranging in concentration from 2990 to 13 200 ng g(-1) (wet wt) in males and from 1910 to 8390 ng g(-1) in females. PCCs consisted of two major components, an octachlorobornane and a nonachlorobornane with gas chromatographic retention times of 1.05 and 1.22, relative to 4,4'-DDE. SigmaPCB concentrations in blubber ranged from 2250 to 7290 ng g(-1) in males and from 894 to 5710 ng g(-1) in females. Seven PCB congeners (tetra-, penta- and hexachlorobiphenyls) accounted for 45% of total PCB (SigmaPCB) in narwhal blubber. Narwhal had 1.4- to 8.6-fold higher ratios of tetra- and pentachlorobiphenyls to PCB-153 (2,2',4,4',5,5'-hexachlorobiphenyl), lower 4,4'-DDE/SigmaDDT ratios and lower proportions of trans-nonachlor to total chlordane components than reported for odontocetes living in more contaminated environments. Mean SigmaPCB concentrations in narwhal were 6- to 15-fold lower than in dolphins from the Canadian east coast and belugas from the St Lawrence River estuary, respectively, while PCC levels were from 4- to about 2-fold lower, and SigmaHCH, dieldrin and SigmaCBz differed by <2-fold. The pattern of organochlorines in narwhal tissues suggests they are exposed to proportionally more volatile compounds, and may have less capacity to metabolize some of these compounds, relative to odontocetes living nearer sources of these contaminants.