Blood plasma clinical-chemical parameters as biomarker endpoints for organohalogen contaminant exposure in Norwegian raptor nestlings.

Raptors are exposed to biomagnifying and toxic organohalogenated compounds (OHCs) such as organochlorines, brominated flame retardants and perfluorinated compounds. To investigate how OHC exposure may affect biochemical pathways we collected blood plasma from Norwegian northern goshawk (n=56), golden eagle (n=12) and white-tailed eagle (n=36) nestlings during three consecutive breeding seasons. We found that blood plasma concentrations of calcium, sodium, creatinine, cholesterol, albumin, total protein, urea, inorganic phosphate, protein:creatinine, urea:creatinine and uric acid:creatinine ratios and liver enzymes ALKP and ALAT were positively correlated to PCBs, chlordanes, p,p'-DDE, HCB, PFCs and/or PBDEs. Total bilirubin and glucose were negatively correlated to PCBs while magnesium and potassium were negatively correlated to HCB and p,p'-DDE. In addition, protein:creatinine and ALAT were also negatively correlated to PCBs and PFCs, respectively. The most significant relationships were found for the highly contaminated northern goshawks and white-tailed eagles. The statistical relationships between OHCs and BCCPs indicate that biochemical pathways could be influenced while it is uncertain if such changes have any health effects. The OHC concentrations were below concentrations causing reproductive toxicity in adults of other raptor species but similar to those of concern for endocrine disruption of thyroid hormones in e.g., bald eagles.

Determination of n-octanol/water partition coefficient for DDT-related compounds by RP-HPLC with a novel dual-point retention time correction.

n-Octanol/water partition coefficients (P) for DDTs and dicofol were determined by reversed-phase high performance liquid chromatography (RP-HPLC) on a C(18) column using methanol-water mixture as mobile phase. A dual-point retention time correction (DP-RTC) was proposed to rectify chromatographic retention time (t(R)) shift resulted from stationary phase aging. Based on this correction, the relationship between logP and logk(w), the logarithm of the retention factor extrapolated to pure water, was investigated for a set of 12 benzene homologues and DDT-related compounds with reliable experimental P as model compounds. A linear regression logP=(1.10±0.04) logk(w) - (0.60±0.17) was established with correlation coefficient R(2) of 0.988, cross-validated correlation coefficient R(cv)(2) of 0.983 and standard deviation (SD) of 0.156. This model was further validated using four verification compounds, naphthalene, biphenyl, 2,2-bis(4-chlorophenyl)-1,1-dichloroethane (p,p'-DDD) and 2,2-bis(4-chlorophenyl)-1,1-dichloroethene (p,p'-DDE) with similar structure to DDT. The RP-HPLC-determined P values showed good consistency with shake-flask (SFM) or slow-stirring (SSM) results, especially for highly hydrophobic compounds with logP in the range of 4-7. Then, the P values for five DDT-related compounds, 2-(2-chlorophenyl)-2-(4-chlorophenyl)-1,1,1-trichloroethane (o,p'-DDT), 2-(2-chlorophenyl)-2-(4-chlorophenyl)-1,1-dichloroethane (o,p'-DDD), 2-(2-chlorophenyl)-2-(4-chlorophenyl)-1,1-dichloroethene (o,p'-DDE), and 2,2,2-trichloro-1,1-bis(4-chlorophenyl)ethanol (dicofol) and its main degradation product 4,4'-dichlorobenzophenone (p,p'-DBP) were evaluated by the improved RP-HPLC method for the first time. The excellent precision with SD less than 0.03 proved that the novel DP-RTC protocol can significantly increases the determination accuracy and reliability of P by RP-HPLC.

Deriving site-specific 2,2-bis(chlorophenyl)-1,1-dichloroethylene quality criteria of water and sediment for protection of common tern populations in Bohai Bay, North China.

In this paper we first present a method of deriving site-specific water and sediment quality criteria of chemicals for protecting wildlife populations. The method has two steps: (1) identification of the threshold concentration in specific tissue corresponding to a population benchmark response and (2) extrapolating quality criteria on the basis of the bioaccumulation in tissue from the water or sediment (e.g., the bioaccumulation factor (BAF) and biota/ sediment accumulation factor (BSAF)). The method was applied to derive 2,2-bis(chlorophenyl)-1,1-dichloroethylene (p,p'-DDE) quality criteria of water and sediment of Bohai Bay, China, for common tern populations. The benchmark concentration in eggs of the common tern was determined to be 663 ng/g wet weight from the relationship curve between concentration (biotic burden in eggs) and the intrinsic rate of population increase (r) calculated by an age-structured matrix approach. The p,p'-DDE concentrations (mean 58.79 and ranging from 13.14 to 326.60 ng/g wet weight) measured in common tern eggs (n = 35), collected from the Beidagang wetland on the coast of Bohai Bay in China, and those in surface water or sediment from literature values were combined to estimate the probability distribution of BAF and BSAF using the Monte Carlo method. Finally, the marine water and sediment quality criteria of p,p'-DDE in Bohai Bay were estimated to be 4 ng/L and 1.9 ng/g dry weight, respectively.