The Environmental Behavior of Methylene-4,4'-dianiline.

Methylene-4,4'-dianiline (MDA, CAS-No. 101-77-9) is a high production volume intermediate that is mainly processed to diisocyanates and finally polyurethanes. This review summarizes available data concerning the environmental behavior. When released into the environment, MDA distributes into water and subsequently sediment and soil compartments; the air is of little relevance, owed to the low vapor pressure and short atmospheric half-life, which renders MDA non-critical for long-range transport. Biodegradation data present a diverged picture; in some tests, MDA is not readily biodegradable or even not inherent biodegradable; in other tests, MDA turned out to be readily biodegradable (but failing the 10-d window). The history and composition of the inoculum used for testing seem to play an important role, which is underlined by good test results with adapted inoculum. In soil, initially a rapid mineralization is observed, which slows down within the first days due to competitive chemical absorption. The latter results in degradation rates comparable to that of natural organic matter. Under anaerobic conditions, mineralization is poor. Irreversible chemisorption occurs unless soils/sediments are highly reduced. Half-lives due to primary decay do not indicate MDA to be persistent according to the regulatory guidance used in then EU, Canada, or the USA; in Japan, however, due to test results in MITI degradation tests, MDA would be regarded as persistent. The identification of microbial MDA metabolites deserves further research. MDA is not bioaccumulative, but it is toxic to aquatic organisms and mammals. MDA in pore water of soils is rapidly adsorbed on the surface of plant roots. Test runs were too short to draw a final conclusion with regards to transport to stem, leaves, and fruits. Data from structurally similar compounds indicate that such transport would account for less than 1% of the root-adsorbed material.

A Review of the Environmental Degradation, Ecotoxicity, and Bioaccumulation Potential of the Low Molecular Weight Polyether Polyol Substances.

"Polyalkylene glycol" is the name given to a broad class of synthetic organic chemicals which are produced by polymerization of one or more alkylene oxide (epoxide) monomers, such as ethylene oxide (EO) and propylene oxide (PO), with various initiator substances which possess amine or alcohol groups. A generalization of this polymerization reaction is illustrated in Fig. 1.

The acute toxicity of nickel to Daphnia magna: predictive capacity of bioavailability models in artificial and natural waters.

The effects of Ca, Mg, Na and pH on the acute toxicity of Ni to Daphnia magna were investigated in a series of 48-h immobilization assays in synthetic test solutions. Both Ca and Mg reduced Ni toxicity, while Na did not. Ni toxicity was not affected in the pH range of 5.7-7.5, but a further increase of pH up to 8.1 resulted in an increase of toxicity of the free Ni2+ ion. Based on the results of these experiments, a biotic ligand model (BLM) was developed in which the effects of Ca and Mg were modeled as single-site competition effects. Stability constants representing the binding strength between Ca2+ and Mg2+ and the biotic ligand (BL) were logK(CaBL)=3.10 and logK(MgBL)=2.47, respectively. The effect of pH could not be appropriately described by single-site competition between Ni2+a nd H+. Since the overall variation of toxicity within the tested pH range was relatively small, we decided not to incorporate the effect of pH in the current model. The model was able to predict 48-h EC50s in all synthetic test solutions by an error less than factor 2. The model's predictive capacity was also evaluated using results of toxicity tests in Ni-spiked natural surface waters. For 15 out of 16 tested waters, 48-h EC50s were predicted by an error less than factor 2. Additionally, after calibration to account for interclonal or interspecies sensitivity differences, the model was able to accurately predict earlier published 48-h EC50s for another D. magna clone as well as for Ceriodaphnia dubia. Finally, the predictive capacity of the model was demonstrated to be better than that of previously proposed models that include a logK(NaBL), a logK(HBL) and a logK(CaBL), but did not incorporate a logK(MgBL). An in-depth comparison of these models learned that (i) there is no need to incorporate a logK(NaBL), (ii) it is important to recognize the protective effect of Mg, and (iii) the incorporation of a logK(HBL) does not adequately describe the effect of pH. Although our model seems very promising, further research, especially into the effects of elevated pH and alkalinity levels, is needed to allow further refinement.

Variability of the protective effect of sodium on the acute toxicity of copper to freshwater cladocerans.

The acute biotic ligand model (BLM) is proposed by the U.S. Environmental Protection Agency (U.S. EPA) to incorporate bioavailability in calculating aquatic life criteria for Cu in freshwater. This approach currently assumes that the effects of water chemistry on acute Cu toxicity can be described with one single set of identical BLM parameters for all organisms. An important water characteristic is the concentration of Na, which protects aquatic organisms against Cu toxicity. Based on physiological considerations related to the mechanism of Cu toxicity and the possible role of Na therein, we hypothesized that an interspecies variability of the protective effect of sodium on Cu toxicity might exist among freshwater organisms. To test this hypothesis, acute 48-h toxicity assays with Cu were conducted with 16 field-collected cladoceran populations and a laboratory-reared clone of Ceriodaphnia dubia at Na concentrations of between 0.077 and 10 mM. Increased Na protected all but one population. Contrary to what the BLM predicts, however, an upper limit to this protective effect was observed for some populations at Na concentrations of greater than 4 mM. This may suggest that processes other than just Cu-Na competition at a single unidentate biotic ligand site may be involved in Cu toxicity. Between populations, conditional stability constants for binding of Na to the biotic ligand (log K*(NaBL)), which quantify the protective effect of Na, varied between 2.2 and 4.4. Higher log K values generally were associated with more sensitive populations. Although a full mechanistic explanation for our observations is lacking, our data may potentially be used to refine the U.S. EPA procedure to establish site-specific water-quality criteria for Cu.

Inter- and intra-species variation in acute zinc tolerance of field-collected cladoceran populations.

Acute zinc toxicity was assessed for 10 freshwater cladoceran species collected in six different ecosystems across Europe and for two standard laboratory-reared species (Daphnia magna and Ceriodaphnia dubia). The collected organisms belonged to five different genera: Daphnia (subgenus Daphnia and Ctenodaphnia), Ceriodaphnia, Simocephalus, Acroperus and Chydorus. The 48-h EC50 of the field-collected organisms tested in standard laboratory water ranged from 375+/-141 to 4314+/-1513 microg Znl(-1). The laboratory clone of D. magna was less sensitive than the majority of the field-collected species, while our laboratory Ceriodaphnia dubia was the second most sensitive. Considerable inter-species variation was found within the genus of Ceriodaphnia (factor 6) and within the genus Daphnia (factor 8). Among the different (sub)genera tested, Chydorus and Ctenodaphnia were significantly more tolerant than the others (up to a factor 3 difference). A significant positive relationship (r2=0.67, p<0.05) between the mean cladoceran 48-h EC50 and the ambient zinc concentration of the different aquatic systems was demonstrated, suggesting a role of acclimation and/or adaptation. No significant correlation between the acute zinc tolerance and the length of the organisms was found.

Multigeneration acclimation of Daphnia magna Straus to different bioavailable copper concentrations.

A large acclimation experiment was performed with Daphnia magna in which two different copper bioavailability (as Cu2+) groups (N and M) were used. In the N group the cupric ion activity increased with increasing dissolved copper-acclimation concentration, while in the M group the ion activity decreased with increasing dissolved copper concentration. The activity of copper carbonates and hydroxides was up to an order of magnitude lower than the cupric ion activity. After five generations of acclimation, the acute copper sensitivity (mean +/- SD) of the N group ranged from 193 /- 24 to 296 +/- 50 microg Cu L(-1) and for the M group from 198 +/- 27 to 315 +/- 38 microg Cu L(-1) for daphnids acclimated to 1 and 100 microg Cu L(-1), respectively. The internal copper concentration of the acclimated daphnids also resulted in similar results between the two groups. Acclimation of the two daphnid groups for five consecutive generations to the three dissolved copper concentrations resulted in a shift in the optimal concentration range toward 1 microg Cu L(-1), using energy reserves as an endpoint. Our results suggest that copper acclimation and accumulation are related to the dissolved copper concentration of the culture medium, but not to the copper activity.

Copper regulation and homeostasis of Daphnia magna and Pseudokirchneriella subcapitata: influence of acclimation.

This study aimed to evaluate (1) the capacity of the green alga Pseudokirchneriella subcapitata and the waterflea Daphnia magna to regulate copper when exposed to environmentally realistic copper concentrations and (2) the influence of multi-generation acclimation to these copper concentrations on copper bioaccumulation and homeostasis. Based on bioconcentration factors, active copper regulation was observed in algae up to 5 microg Cu L(-1) and in daphnids up to 35 mug Cu L(-1). Constant body copper concentrations (13+/-4 microg Cu g DW(-1)) were observed in algae exposed to 1 through 5 microg Cu L(-1) and in daphnids exposed to 1 through 12 microg Cu L(-1). At higher exposure concentrations, there was an increase in internal body copper concentration, while no increase was observed in bioconcentration factors, suggesting the presence of a storage mechanism. At copper concentrations of 100 microg Cu L(-1) (P. subcapitata) and 150 microg Cu L(-1) (D. magna), the significant increases observed in body copper concentrations and in bioconcentration factors may be related to a failure of this regulation mechanism. For both organisms, internal body copper concentrations lower than 13 microg Cu g DW(-1) may result in copper deficiency. For P. subcapitata acclimated to 0.5 and 100 microg Cu L(-1), body copper concentrations ranged (mean+/-standard deviation) between 5+/-2 microg Cu g DW(-1) and 1300+/-197 microg Cu g DW(-1), respectively. For D. magna, this value ranged between 9+/-2 microg Cu g DW(-1) and 175+/-17 microg Cu g DW(-1) for daphnids acclimated to 0.5 and 150 microg Cu L(-1). Multi-generation acclimation to copper concentrations >or =12 microg Cu L(-1) resulted in a decrease (up to 40%) in body copper concentrations for both organisms compared to the body copper concentration of the first generation. It can be concluded that there is an indication that P. subcapitata and D. magna can regulate their whole body copper concentration to maintain copper homeostasis within their optimal copper range and acclimation enhances these mechanisms.

Copper toxicity to different field-collected cladoceran species: intra- and inter-species sensitivity.

The acute copper sensitivity of 44 European freshwater cladocerans, from four families (Daphniidae, Bosminidae, Macrothricidae, Chydoridae) and 13 genera (Daphnia, Ctenodaphnia, Ceriodaphnia, Simocephalus, Scapholeberis, Bosmina, Acantholeberis, Alona, Acroperus, Chydorus, Eurycercus, Disparalona and Pleuroxus) were assayed. The 48-h EC(50)s of field-collected organisms tested in reconstituted standard laboratory water ranged from 5.3 to 70.6 mug Cu L(-1). Only among Ctenodaphnia were significant intra-species differences observed. Significant inter-species differences were noted among Alonina and Daphnia. Between all genera tested, a maximum of a 12-fold difference in copper sensitivity was noted. Most animals were more sensitive than a laboratory D. magna clone. A weak non-significant increasing trend was noted between mean cladoceran 48-h EC(50) and ambient copper concentration of the different aquatic systems, suggesting acclimation/adaptation in the field. A positive relationship was also observed between the 48-h EC(50) of the field-collected cladoceran species (without the Chydoridae family) and the size of the organisms.

Field validation of sediment zinc toxicity.

A field study was conducted to validate concentrations of zinc in freshwater sediments that are tolerated by benthic macroinvertebrate communities and to determine whether a relationship exists with the acid volatile sulfide (AVS)-simultaneously extracted metal (SEM) model. In both the lake and riverine systems, one sediment type was high in AVS and one low in AVS, which resulted in zinc-spiked sediments that ranged from low to high SEM to AVS ratios. The colonization trays were sampled seasonally, ranging from 6 to 37 weeks of exposure, and were evaluated using several appropriate benthic indices. Results of the field evaluations at the four test sites confirmed the validity of the AVS-SEM model, predicting benthic macroinvertebrate effects correctly 92% of the time. In sediments where the SEM to AVS ratio or the AVS and organic (OC)-normalized fractions exceeded 8 and 583 micromol/g of OC, toxicity was observed from the zinc-spiked sediments. Conversely, when the SEM to AVS ratio or OC-normalized AVS fractions were less than 2 or 100 micromol/g of OC, no toxicity was observed. In the range of 148 to 154 micromol/g of OC, toxicity varied in two treatments. Total zinc concentrations in sediments showed no relationship to benthic effects. The most impaired benthic community occurred in the high-gradient stream sediments, which had low OC and AVS concentrations and SEM to AVS ratios of 33 and 44 in the spiked sediments. Five to six benthic metrics were depressed at SEM to AVS ratios of 8.32 and 9.73. The no-observed-effect level appeared to be near a SEM to AVS ratio of 2, with slight to no effects between ratios of 2.34 and 2.94. No sites with ratios of less than 2 showed any adverse effects.

Relevance of generic and site-specific species sensitivity distributions in the current risk assessment procedures for copper and zinc.

Species sensitivity distributions (SSD) were constructed using acute toxicity data of various cladoceran species collected in five different aquatic systems. The aim of this research was to study the relative acute cladoceran community sensitivity in different aquatic systems. Current risk assessment procedures are based upon hypothetical communities and do not take into account variation in species composition and tolerance between aquatic communities. Two metals, copper and zinc, were used as model toxicants. To establish comparative sensitivity, a standard medium (International Organization for Standardization [ISO]) was used. The generic SSD (log-normal distribution) based on toxicity data obtained in this standard medium for all species (collected at all sites) resulted in a hazardous concentrations that protects 95% of the species occurring in a (hypothetical) ecosystem (i.e., hazardous concentration protecting 95% of the species of the hypothetical ecosystem [HC5]) of 6.7 microg Cu L(-1) (90% confidence limits: 4.2-10.8) and 559 microg Zn L(-1) (375-843). This generic SSD was not significantly different from the site-specific SSDs (i.e., constructed with species only occurring at a specific site). Mean community sensitivity (the geometric mean of 48-h 50% effective concentration [EC50] values of species within a community) among sites varied within a factor of 2 (between 17.3 and 23.6 microg Cu L(-1) for Cu and between 973 and 1,808 microg Zn L(-1) for Zn), and HC5s varied within a factor of 4 for copper (between 4.5 and 17.3 microg Cu L(-1)) and 7 for zinc (between 194 and 1,341 microg Zn L(-1)). For copper, the HC50 of our generic SSD was significantly lower than the one based on literature toxicity data of cladoceran species (which were recalculated to the hardness of our standard medium). In contrast, no significant differences were observed between the generic SSD and the literature-based SSD for zinc. It is suggested that the community sensitivity of different cladoceran populations is similar among aquatic systems and is not dependent on the species composition.

Using the biotic ligand model for predicting the acute sensitivity of cladoceran dominated communities to copper in natural surface waters.

In this study, the acute copper sensitivity of field-collected cladoceran species was determined using their natural surface waters and a standard reconstituted test water as test medium. A total of 43 species were collected on two occasions from six different sites, representing different water types and chemistries in Europe. The collected species belonged to four different families (Daphniidae, Bosminidae, Macrothricidae, Chydoridae) and 11 different genera (Daphnia, Ctenodaphnia, Ceriodaphnia, Simocephalus, Scapholeberis, Alona, Acroperus, Chydorus, Eurycercus, Disparalona, Pleuroxus). In acute experiments with immobilization as end point, the 48-h median effective concentrations (48-h EC50) for the cladoceran species ranged from 5.30 to 70.6 microg of Cu L(-1) in standard test water and from 9.60 to 853 microg of Cu L(-1) in natural waters. The mean site sensitivity (the geometric mean of 48-h EC50 values of species within a community) ranged from 10.1 to 27.4 microg of Cu L(-1) in standard water and from 16.4 to 281 microg of Cu L(-1) in natural water. This indicates that bioavailability is more importantthan inter-community (species composition) differences in determining the variability of copper toxicity across different aquatic systems. For the four surface waters that had a pH within the range for which the acute Daphnia magna biotic ligand model (BLM) has previously been successfully validated, the BLM predicted 48-h EC50 values for 27 of the 28 tested cladoceran species within factor of 2 of the observed values. For the same sites, all community sensitivities were predicted within a factor of 2.3. The BLM was clearly over-protective for the two acidic surface waters tested. Hence, the BLM can be considered a valuable tool for estimating the potentially harmful effects of copperto natural cladoceran communities, but more research will be needed for acidic surface waters.

Influence of multigeneration acclimation to copper on tolerance, energy reserves, and homeostasis of Daphnia magna straus.

A multigeneration acclimation experiment was performed with Daphnia magna exposed to copper to assess possible changes in tolerance and to establish the optimal concentration range (OCEE) of this species. The hypothesis was tested that as the bioavailable background concentration of an essential metal increases (within realistic limits), the natural tolerance (to the metal) of the acclimated/adapted organisms and communities will increase. During 18 months the daphnids were exposed to six different, environmentally relevant, copper background concentrations ranging between 0.5 and 100 microg Cu L(-1) (7 x 10(-15) and 3.7 x 10(-9) M Cu2+). An increase in acute (effect concentration resulting in 50% immobility: 48-h EC50) and chronic copper (effect concentration resulting in 50% or 10% reproduction reduction: 21-d EC50, 21-d EC10) tolerance was observed with increasing exposure concentration. The 48-h EC50 increased significantly from 204 +/- 24 microg Cu L(-1) to 320 +/- 43 microg Cu L(-1). A nonsignificant change from 48.0 (47.9-48.0) microg Cu L(-1) to 78.8 (66.3-93.6) microg Cu L(-1) was noted in the chronic toxicity assays. The optimal concentration range was assessed using different biological parameters (i.e., net reproduction [R0]), energy reserves (Ea), body length measurements, filtration rates, and body burdens. After three generations of acclimation the OCEE ranged between 1 and 35 microg Cu L(-1) (2 X 10(-14) to 80 x 10(-12) M Cu2+). Body burden measurements revealed an active copper regulation up to 35 microg Cu L(-1) (80 pM Cu2+). It can be concluded that acclimation of D. magna to copper does occur in laboratory experiments, even at realistic copper background concentrations (10(-11) - 10(-9) M Cu2+). However, it is suggested that this phenomenon is of less importance in the context of regulatory risk assessments. An optimal copper concentration range for D. magna was observed between 1 and 35 microg Cu L(-1) (10(-14) - 10(-11) M Cu2+), indicating that copper deficiency can occur in routine laboratory cultures.

Long-term acclimation of Pseudokirchneriella subcapitata (Korshikov) Hindak to different copper concentrations: changes in tolerance and physiology.

The effect of long-term copper acclimation of the freshwater green algae Pseudokirchneriella subcapitata to copper was investigated using different physiological and toxicological endpoints. The algae were exposed to seven-five of which are ecologically relevant for European surface waters-copper concentration ranging from 0.5 to 100 microgCul(-1) during a 3-month period. A standard medium was used as culture and test medium with an addition of 2 mg DOCl(-1) (replacing EDTA). At certain intervals, experiments were performed to assess algal biomass, growth rate, chlorophyll and carotenoid content, pigment diversity, autotrophic index, intracellular and adsorbed copper, and the sensitivity of the algae to copper. Chronic copper tolerance (mean +/- standard deviation) increased significantly from 88 +/- 15 to 124 +/- 25 microg Cul(-1) for P. subcapitata acclimated to 0.5 and 100 microg Cul(-1), respectively. Based on the algal biomass, the growth rate, the pigment diversity and the autotrophic index, an optimal concentration range was observed between 1 and 35 microg Cul(-1). Significant decreases in algal biomass, pigment diversity and autotrophic index were observed in algal cultures acclimated to 0.5 microg Cul(-1) and 100 microg Cul(-1). Chlorophyll a content (mean +/- standard deviation) increased from 8.4 +/- 3.1 to 28.6 +/- 7.5 x 10(-14) g per cell and carotenoid content (mean +/- standard deviation) increased from 3.7 +/- 0.8 to 7.1 +/- 1.2 x 10(-14) g per cell for algae exposed to 1 and 100 microg Cul(-1), respectively. Intracellular copper increased from 0.099 to 20.6 x 10(-15) g Cu per cell and adsorbed copper increased from 0.026 to 1.8 x 10(-15) g Cu per cell for algae acclimated for 12 weeks to 0.5 and 100 microg Cul(-1), respectively. This research demonstrates that the use of standard culture media, some of which may be deficient in copper, can result in sub-optimal performance of the organisms, which in turn may affect toxicity test results. Additionally, this work also established an optimal concentration range for copper for this algal species. This phenomenon should be taken in consideration when performing environmental risk assessments of essential elements.

Acclimation of Daphnia magna to environmentally realistic copper concentrations.

It may be hypothesised that as the bioavailable background concentration of an essential metal increases (within natural limits), the natural tolerance (to the metal) of the acclimated/adapted organisms and communities will increase. In this study the influence of acclimation to different copper concentrations on the sensitivity of the freshwater cladoceran Daphnia magna Straus was investigated. D. magna was acclimated over three generations to environmentally relevant copper concentrations ranging from 0.5 to 100 microg Cu/l (copper activity: 7.18 x 10(-15) to 3700 x 10(-12) M Cu2+). A modified standard test medium was used as culture and test medium. Medium modifications were: reduced hardness (lowered to 180 mg CaCO3/l) and addition of Aldrich humic acid at a concentration of 5 mg DOC/l (instead of EDTA). The effects of acclimation on these organisms were monitored using acute mortality assays and long-term assays in which life table parameters, copper body concentrations and energy reserves were used as test endpoints. Our results showed a two-fold increase in acute copper tolerance with increasing acclimation concentration for second and third generation organisms. Copper acclimation concentrations up to 35 microg Cu/l (80 pM Cu2+) did not affect the net reproduction and the intrinsic growth rate. The energy reserves of the acclimated daphnids revealed an Optimal Concentration range (OCEE) and concentrations between 5 and 12 microg Cu/l (0.5-4.1 pM Cu2+) and 1 and 35 microg Cu/l (0.023-80 pM Cu2+) seemed to be optimal for first and third generation daphnids, respectively. Lower and higher copper concentrations resulted in deficiency and toxicity responses. It was also demonstrated that up to 35 microg Cu/l, third generation daphnids were able to regulate their total copper body concentration. These results clearly indicate that bioavailable background copper concentrations present in culture media have to be considered in the evaluation of toxicity test results, especially when the toxicity data are used for water quality guideline derivation and/or ecological risk assessment for metals.

Tolerance and acclimation to zinc of field-collected Daphnia magna populations.

The zinc tolerance of two Daphnia magna populations collected at a zinc contaminated site was studied. One clone was isolated from each population in order to determine interclonal variation in zinc tolerance. 48hEC50-values, life table parameters, carapace lengths and cellular energy allocation (CEA) were used as test endpoints and compared with the results obtained with a standard laboratory clone. The natural clones were more tolerant to acute zinc toxicity (up to a factor of 4) and exhibited a higher reproduction rate (factor 2) and carapace length (factor 1.2). The optimal zinc concentrations for the natural clones ranged from 80 to 200 microg Zn/l. When cultured without zinc, the natural clones gradually lost their zinc tolerance. Therefore, the environmental relevance of using toxicity data obtained with organisms (natural, as well as laboratory clones) acclimated to culture media containing no or very small amounts of zinc can be questioned.